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Thermoelectric prospects of chemically deposited PbSe and SnSe thin

films
To cite this article before publication: P. K. Nair et al 2018 Semicond. Sci. Technol. in press https://doi.org/10.1088/1361-6641/aaa592

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Page 1 of 24 AUTHOR SUBMITTED MANUSCRIPT - SST-104282.R1

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5 Thermoelectric prospects of chemically deposited PbSe and SnSe thin films
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7 P. K. Nair, Ana Karen Martínez, Ana Rosa García Angelmo, Enue Barrios Salgado, M. T. S. Nair
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9 Instituto de Energía Renovables, Universidad Nacional Autónoma de México, Temixco, Morelos –

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10 62580, México; pkn@ier.unam.mx
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13 Abstract:
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15 Thin films of PbSe, of 400-600 nm in thickness, were obtained via chemical deposition from
16 a solution containing lead nitrate, thiourea and selenosufate. SnSe thin films of 90 – 180 nm in

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17
18 thickness, were also obtained by chemical deposition from a solution containing selenosulfate.
19 Optical and electrical properties of these thin films were significantly altered by heating them in
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selenium vapor at 300 oC. Thin film PbSe has a bandgap (Eg) of 1.17 eV (direct gap, forbidden
21
22 transitions), which decreases to 0.77 eV when it has been heated. Its electrical conductivity (σ) is p-
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type: 0.18 Ω-1 cm-1 (as-prepared), and 6.4 Ω-1 cm-1 when heated. Thin film SnSe is of orthorhombic
crystalline structure which remains stable when heated at 300 oC, but its Eg increases from 1.12 eV
(indirect) in as-prepared film to 1.5 eV (direct, forbidden transitions) upon heating. Its electrical
conductivity is p-type, which increases from 0.3 Ω-1 cm-1 (as-prepared) to 1 Ω-1 cm-1 when heated
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29 (without Se-vapor). When SnSe film is heated at 300 oC in presence of Se-vapor, they transform to
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SnSe2, with Eg of 1.5 eV (direct, forbidden) with n-type electrical conductivity, 11 Ω-1 cm-1. Seebeck
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32 coefficient for the PbSe films is: + 0.55 mV/K (as prepared) and +0.275 mV/K (heated); for SnSe films
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it is: + 0.3 mV/K (as prepared) and +0.20 mV/K (heated); and for SnSe2 film, - 0.35 mV/K. A five-
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35 element PbSe-SnSe2-PbSe-SnSe2-PbSe thermoelectric device demonstrated 50 mV for a
36 temperature difference ΔT = 20 oC (2.5 mV/K). For SnSe-SnSe2-SnSe-SnSe2-SnSe device, the value
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38 is 15 mV for ΔT = 20 oC (0.75 mV/K). Prospect of these thin films in thermoelectric devices of hybrid
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39 materials, in which the coatings may be applied on distinct substrate and geometries is attractive.
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43 Key words: Thermoelectrics, thermoelectric elements, thermoelectricity; PbSe thin films; SnS thin
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45 films; SnSe2 thin films; chemical deposition
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5 1. Introduction
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8 Chemically deposited lead selenide (PbSe) thin film has been used since the 1950’s in infrared
9 detectors due to their small bandgap (Eg) 0.26 eV [1]. Much larger Eg (> 1 eV) of PbSe in nanocrystals

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10
11 led to applications in solar cells in the 2000’s [2, 3]. They have also been recognized among
12 thermoelectric materials [4]. Chemically deposited SnSe thin film has been viewed with interest for
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14 solar cells due to their Eg of 1 eV, but its prospects as thermoelectric material also has been
15 highlighted in 2014 [5]. The feasibility of forming thermoelectric devices from p-type SnSe thin films
16

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and n-type SnSe2 thin films, produced by heating chemically deposited SnSe in Se-vapor, has been
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18 demonstrated in 2016 [6]. Such background shared by PbSe, SnSe, and SnSe2 becomes relevant
19 for thermoelectric and thermal interface materials for energy recovery from natural resources and
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21 industrial processes; for heating and cooling; and for technology development in photonic and
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electronic devices, as highlighted in a 2017 update [7].

In thermoelectrics, the dimensionless figure of merit (ZT) for a particular material at an

application temperature (T) is given as (σS2T)/κ, where σ is its electrical conductivity; S, the Seebeck
coefficient; and κ, the thermal conductivity (κe + κl) has electronic (e) and lattice (l) contributions; and
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29 Z = (σS2)/κ of a material [4]. The internal resistance of the thermoelectric device (R) should be low for
30 efficient power generation across a load RL = R [8]. This calls for electrical conductivity of 103 Ω-1 cm-
31 1 or higher for the thermoelectric element. The value of S, is approximately [9]: S = 86(μV/K) {ln[(Nc
32
33 or Nv)/(nn or pp)]}, where Nc, Nv is taken as 1019 cm-3 for an order of magnitude calculation for the
34 specific density of states for conduction (Nc) or valence (Nv) band of semiconductors of n-type or p-
35
36 type electrical conductivity with majority carrier concentration nn or pp [10]. The value 86 μV/K is the
37 ratio of Boltzmann constant (k B, 1.38x10-23 J/K) to the charge of electron (q, 1.60x10-19 C). An
38
increase of nn or pp leads to a high σ, but entails a reduction in S. Further, the thermal conductivity
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40 due to free-carriers (κe) would be high for high-σ material causing a lowering of ZT. This makes
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42 investigation in thermoelectric materials challenging, which had kept viable semiconductor materials
43 for thermoelectric p-n couples to just three, well into the 1980´s: Bi2Te3, PbTe, and Ge, with ZT barely
44
above 0.5 [4, 8].
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A means of keeping ZT high for a material is to seek in it a low value for the lattice (phonon
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48 scattering) component of the thermal conductivity. This was found to be the case along a specific
49
lattice vector for SnSe (orthorhombic) single crystal, where a ZT of 2.5 has been reported for T = 750
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51 K; σ, 104 Ω-1 m-1 (100 Ω-1 cm-1); S, 0.35 mV/K; and κ, 0.4 W m-1 K-1 [5]. By comparison, ZT for PbSe
52 single crystal is comparatively lower, at 1.5, close to that of the well-known thermoelectric materials,
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54 PbTe and Bi2Te3 reached in special cases by 2010 [4]. Research in novel thermoelectric materials
55 seek out a high ZT at the temperature interval of the application. Alternatively, it could be based on
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3 device cost per watt, aiming to reduce it from US$1 – 2 per Watt toward 5 % of it [4]. Theoretical
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limitation of dual-dopable (n/p) single or nanocrystal, may be overcome in composite and hybrid
5
6 materials, with flexibility in designs of micro- and wearable devices offering price reduction [11].
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8 Chemical deposition of semiconductor thin films on substrates of distinct thermal and
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electrical characteristics is a prospective approach toward eventual large-scale thermoelectric
10
11 applications. Cost, “earth-abundant” availability, and toxicity, as considered for photovoltaic materials
12 for large-scale development [12, 13] will become important selection criteria for thermoelectric
13
14 counterparts as well. That trend has already set-in while recommending SnTe to replace PbTe (toxic
15 and scarce) with comparable ZT of 1.6 [14]. Low-κl materials such as Sn2S3 and cubic-structured SnS
16

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17 have come out even superior to SnSe in theoretical models [15]. Stacks of cubic structured SnS-
18 SnSe thin films heated at 300 oC was found to offer σ-values attractive for thermoelectric applications
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20 [16]. Large-span of SnS-SnSe-SnTe orthorhombic (or rock salt) solid solutions have been studied
21 because of their general prospects as semiconductors, prior to the new-found interest in
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thermoelectrics [17]. In this work we present the deposition technique, post-deposition processing,
and characteristics of p-type PbSe and p-type SnSe thin films suitable for such adaptation. Thin films
of n-type SnSe2 were produced by heating SnSe in Se-vapor. Performance of thermocouple elements
of p-PbSe/n-SnSe2 and p-SnSe/n-SnSe2 are illustrated. Overall prospects of these materials as well
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as other thin films for development of thermoelectric applications on distinct substrates are
29
30 considered.
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34 2. Experimental details
35
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37 Substrate pretreatment: Thin films were deposited on Corning microscope glass slides (25 mm x 75
38 mm x 1mm – thickness), which were cleaned in neutral soap solution and immersed overnight at
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40 room temperature in a dilute Na2S solution of 1.5 g of Na2S ∙ 9H2O from Aldrich in 100 ml of deionized
41 water. This procedure leads to the deposition of adherent and compact thin films in chemical
42
43 deposition, as discussed previously for SnSe film [6, 18]. The procedure has been found beneficial in
44 chemical deposition of semiconductor films; and is routinely used for PbSe and SnSe deposition in
45
46 our laboratory. A systematic study of the mechanisms underlying this surface modification is not yet
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47 available, other than at an intuitive level, in which the presence of adsorbed S or SH– layer on the
48
glass substrate has been proposed [18]. These pretreated substrates were rinsed in de-ionized water,
49
50 left to dry and were promptly used for the deposition of thin films. By the following day the benefit of
51 this substrate-pretreatment is no longer perceived.
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Selenosulfate solution for metal selenide semiconductor deposition: Preparation of semiconductor
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55 thin films from a solution of Na2SeSO3 (SSS – sodium selenosulfate) has been established by 1969
56 [19]. For the present work on PbSe and SnSe thin films, an SSS solution of approximately 0.2 mol
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3 dm-3 (M) in concentration was prepared by refluxing 2 g of Se-powder (ASARCO) and 12.3 g Na2SO3
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(Aldrich) in 100 ml deionized water, as described in [6, 18]. This composition would leave an excess
5
6 of [SO3]2 – in the solution, which would inhibit the conversion of Se2 – to elemental Se when in contact
7
with atmospheric oxygen (Se2– + O2 → Se + O22–) during metal selenide deposition [1]. This condition
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9 promotes the deposition of a specularly reflective film of PbSe (Pb2+ + Se2 – → PbSe). The dissociation

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10 of SeSO32 – to Se2– in chemical solution deposition of metal selenide semiconductor thin films is
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12 discussed in [20]. It is worth noting that from a SSS solution of pH 4.5 good quality elemental Se thin
13 film may be obtained, which when heated in contact with metal films produces metal selenide thin
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15 films including SnSe2 and SnSe [21, 22].
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17 PbSe thin films: A deposition solution 100 mL in volume contained 14 mL of 0.5 M solution of lead
18 nitrate, 20 mL of 1 M solution of NaOH, 10 mL of 1 M triethanolamine (TEA – (CH2CH2OH)3N)), 5.5
19
20 mL of the SSS solution, 0.5 mL of 1 M solution of thiourea (TU) and 50 mL of deionized water. The
21 starting solution is clear and transparent. All reagents were of laboratory grade from Sigma-Aldrich
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or ‘Baker Analyzed.’ We previously reported on PbSe films made using SSS or dimethylselenourea
(DMSU) [23] for solar cells. The simultaneous presence of TU and SSS in the solution lets TU play a
role as complexing agent, thereby regulating the reaction and leading to the deposition of specularly
reflective PbSe films. The quality of PbSe film made this way with SSS is usually possible only when
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DMSU is used [23, 24]. The pH of the starting solution was nearly 14. The deposition of PbSe film
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30 was made on glass slides treated in Na2S, first for 30 min at 60 oC in a circulation bath resulting in a
31 reflective silvery film of thickness 40-50 nm. Subsequently the deposition proceeded for 9 h or 19 h
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(overnight) at 30 oC, resulting in film thickness of 400 nm and 600 nm, respectively. Deposition at a
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34 lower temperature this way gave smooth specularly reflective films with a higher band gap (1.17 eV)
35 than the bulk value (0.26 eV). In chemically deposited PbSe films, it is known that Eg can be raised
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37 above 1 eV if the crystallite diameter in thin films falls below 20 nm [25] because it would be less than
38 the exciton Bohr diameter of 46 nm, thereby setting-in strong quantum confinement.
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40 SnSe thin films [6, 18]: To prepare 80 mL deposition solution, 0.7 g of SnCl2 (anhydrous, Aldrich) was
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42 dissolved in 5 mL of acetone in a 100 mL beaker and added with stirring the following: 30 mL of 3.5
43 M TEA, 18 mL of 1 M solution of NaOH, 0.25 mL of 0.5 % polyvinyl pyrrolidone (PVP) w/w solution in
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45 water, 4.0 mL of the SSS-solution, and the rest, water. Reagents were from Sigma-Aldrich or ‘Baker
46 Analyzed’. PVP solution contributes toward better quality for tin selenide thin films, as originally
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proposed in [26] for SnSe thin film deposition. Initial pH of this deposition bath was nearly 14. The
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49 Na2S-pretreated glass slides were immersed in this solution and placed in a circulation bath
50
maintained at 17 oC. After 3 h 30 min (210 min), a film 90 nm in thickness was deposited, and a
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52 repeat-deposition from fresh bath increased it to 180 nm. The films were specularly reflective.
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54 Heating the films: For PbSe films, this was done at 300 oC for 30 min at a nitrogen pressure of 20
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Torr in two ways: (i) by keeping the coated slides with the films, 400 and 600 nm in thickness in a
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3 petri dish wrapped in aluminum foil; and (ii) by adding 5 mg Se powder (Sigma-Aldrich) inside such a
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petri dish containing the two slides and wrapping it with aluminum foil. The heating had two purposes
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6 – in (i) to stabilize the films for thermoelectric applications at working temperature exceeding 150 oC
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and (ii) to improve the electrical conductivity through improved charge carrier mobility broght-in
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9 through crystallization and grain-growth and/or increased hole-concentration (pp).

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11 Heating of SnSe thin films (90 and 180 nm in thickness) was done as in (i) for PbSe films.
12 However, heating the films in the presence of Se powder at such temperature had the purpose of
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14 converting the films to n-type SnSe2 through the reaction [6]:
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16 SnSe + Se → SnSe2 (1).

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17 100 nm 0.13 mg/cm2 (300-400 °C) 145 nm
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19 Thin film of SnSe2 produced this way remained stable n-type during further heating at temperatures
20 up to 430 oC [6].
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Characterization of the films: Thickness of the films was measured on an Ambios Technology XP-
200. Change in the relative composition of the elements in films brought-in through heating the film
was done in an energy dispersive spectral analyzer (EDS) attachment to a Hitachi SU1510 Scanning
electron microscope (SEM). For doing this, the excitation voltage was kept at 7 keV to inhibit emission
lines from the glass substrate. X-ray diffraction (XRD) measurements on the films were done in the
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grazing incidence (GIXRD) mode with grazing angle δ = 2.5° on Rigaku ULTIMA IV using Cu-Kα
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31 radiation. The optical transmittance (T – air as reference) and specular reflectance (R – front
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aluminized mirror as reference) spectra of the films were recorded in the 350 – 2500 nm spectral
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34 range on a Shimadzu 3600 UV–VIS-NIR spectrophotometer. The light beam made incidence on the
35 film-side. Pairs of silver-paint electrodes (DuPont PV428) of 10 mm in length at 10 mm separation
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37 applied on the film surface allowed a bias of 20 V to be applied for on-plane current and σ -
38 measurement. The sample was first stabilized in the dark and then current was measured for 30 s in
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40 the dark, 30 s under 850 W/m2 intensity of illumination from a tungsten-halogen lamp, and a final 30
41 s in the dark. For the thermoelectric measurements, a small strip of the film (0.8 cm X 2.5 cm on the
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1 mm glass) was cut and placed across differentially heated copper blocks. Voltage across the film
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44 (V) was measured as a function of the differential temperature ΔT in the temperature interval 20 – 50
45 oC. The differential temperature was provided by heating/cooling produced on two thermoelectric
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47 devices. Thermoelectric couples were constituted by five thin film elements: (hot) p-n-p-n-p (cold)
48 sequence prepared using carbon-paint interconnection. Voltage across the p(hot)/p(cold) elements
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50 was measured for ΔT up to 20 oC (K). Following thin films and thermocouple devices were studied:
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52 1 PbSe 600 nm; 2 PbSe 400 nm;
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53 3 PbSe 400 nm 300 C – Se; 4 PbSe 600 nm 300 C – Se; 5 PbSe 600 nm 300 C;
54 6 SnSe 180 nm; 7 SnSe 180 nm 300 C;
55 8 SnSe2 185 nm; 9 SnSe2 100 nm.
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3 Samples 8 and 9 were of n-type. Thermocouple devices were made by connecting five p-n-p-n-p film
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strips: 3 – 8; 1 – 8; 4 – 8; 7 – 8; and 3 – 9. The order in which the sample numbers are presented are
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6 in descending order of Seebeck coefficient (seen in section 3.5).
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10 3. Results and discussion
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12 3.1. Chemical compositional change upon heating
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14 In the EDS result of the films in Figure 1 (a) is seen that the relative intensities of Pb – Mα1,2
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16 emission at 2.342 keV and Se-Lα1,2 at 1.379 keV are nearly the same for PbSe thin film of 600 nm

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17 thickness (as prepared) shown in the bottom plot and after it had been heated at 300 oC (middle plot).
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19 Except for Na-Kα emission at 1.041 keV arising from the glass substrate, all observed peaks are
20 accounted for by emission from Pb and Se of the thin film. The top plot illustrates that heating the film
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22 at 300 oC in Se vapor leads to a definite increase in the intensity of Se-Lα1,2 peak. Since the p-type σ
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of PbSe arises from vacancies in Pb – sites relative to Se, such increase in Se in the film drawn from
the vapor phase would increase the hole-concentration (pp) and hence its σ. This is indeed the case,
as will be seen in section 3.4. Even though TU was used in the preparation of the film, no detectable
presence of S-Kα1,2 emission at 2.31 keV is perceived – the shape of Pb-Mα,β peak remains unaltered
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29 upon heating.
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31 In Figure 1 b), the intensity of Se-Lα1,2 emission peak at 1.379 keV is seen increased by a
32 factor of two after the film has been heated at 300 oC in presence of Se vapor, described in equation
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34 (1), suggesting the formation of SnSe2. Since SnSe and SnSe2 films are relatively thinner, 180 – 185
35 nm, and are of an element of lower atomic number (Sn, 50 compared with Pb, 82), emission peaks
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37 of Si and Na from the glass substrates are seen more pronounced relative to that of Sn.
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41 3.2. Crystalline structure
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PbSe thin film: Figure 2 b) – f) shows GIXRD patterns for PbSe films of 600 nm in thickness and a
45
46 comparison of these with the peak positions and relative intensities in the powder diffraction file (PDF
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78-1903) for PbSe, given in Figure 2 a). The relative intensity in the PDF for diffraction from (111)
48
49 planes of PbSe is 37 %, whereas in the PbSe thin film in Figure 2 b) it is unnoticeably small, 3-5 %.
50 Most other peaks too are barely noted. Hence in Figures d), e), and f) normalized intensity of the
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52 diffraction patterns is given in log-scale. This way, diffraction peaks for rock-salt structure of all-even
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3 Figure 2 c) is a zoom-in on the (200) peaks of PbSe given in Figure 2 d), e) and f). For the
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film heated at 300 oC in Se vapor, there is an exact match of the peak position with that of the standard
5
6 pattern. The slight shift to the right of the observed diffraction peak for the as-prepared and heated
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films may suggest incorporation of very small quantity of S (from TU) in the film. Such S-sites in the
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9 unit cells of the film may be replaced by Se when it has been heated at 300 oC in Se-vapor. The inter-

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10 planar distance d(200) for PbSe is 3.061 Å and for PbS, it is 2.969 Å. The observed value for d(200) in
11
12 the as-prepared film is 3.054 Å. This suggests the formation of a solid solution PbS0.07Se0.93, but with
13 a composition very close to PbSe. When S2- (from TU) and Se2- (from SSS) are present in solution
14
15 containing Pb2+ (from lead nitrate), PbSe is readily formed because its solubility product (10-37 mol2
16 dm-6) is much smaller than that of PbS (10-28 mol2 dm-6) [20]. For thermoelectric applications, we

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17
would prefer the film heated in Se-vapor (which is indeed PbSe), because of its higher σ. The
18
19 crystalline grain diameter evaluated from Scherrer-formula is 15 nm for the as-prepared or heated
20 PbSe film and nearly 19 nm in the film heated at 300 oC with Se-vapor. Thus, grain growth is assisted
21
22 by the addition of Se through the inter-grain region. In all these cases, the crystalline grain diameter
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(0.26 eV) are expected for these films.
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is less than the exciton Bohr radius in PbSe, estimated at 40-80 nm, depending on the effective mass
for electron-hole [24]. Hence strong quantum confinement and Eg much higher than the bulk value
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Texture coefficient (TC) for crystalline planes (hkl) of the material giving rise to a particular
29
30 diffraction peak is defined by: [I(hkl)/Io(hkl)]/{(1/N)ΣN [I(hkl)/Io(hkl)]}. Here, N is the number of (hkl) diffraction
31 peaks with observed relative intensity I(hkl), and with Io(hkl) in the (star quality) powder diffraction file,
32
33 being considered in the analysis. When crystalline grains in a particular sample are randomly oriented
34 as in an ideal crystalline powder sample, TC for any (hkl) is unity; otherwise it would be distinct. For
35
36 diffraction from (200) planes TC is 3.4 for as-prepared PbSe film, which increased to 3.9 when the
37 film has been heated in Se-vapor, seen listed in the side-panels. For PbSe film deposited from DMSU
38
(instead of from SSS) deposited at 40 – 60 oC, the strong preferential orientation with TC > 3 occurs
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40 for diffraction from (111) planes [25]. The temperature of deposition and solution composition greatly
41
affects the orientation of crystalline planes in PbSe films. The absence of TU in the deposition bath
42
43 produced PbSe thin films at 60 oC without any preferential orientation, and so was the case with films
44 deposited from DMSU at 26 oC [23].
45
46 SnSe and SnSe2 thin films: Figure 3a) shows the PDF 89-0232 of orthorhombic SnSe, which is a
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48 good match for the GIXRD pattern for the SnSe thin film in Figure 3b). The crystalline grain diameter
49 of 19 nm for the thin film material is estimated from the de-convoluted diffraction peak for (111) planes,
50
51 shown in the inset. Heating of the film at 300 oC does not lead to an increase in crystalline diameter
52 (18 nm), as described in the inset of Figure 3c). There is an indication of the formation of SnSe2,
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54 which occurs due to an excess of Se in this chemically deposited film: the diffraction peak (*) from
55 (001) planes of this constituent material makes its presence. A replot of the data in log-scale in
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3 intensity shown in Figure 3d) illustrates that except for the (001) peak of SnSe 2 as a minor component,
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all the diffraction peaks belong to SnSe. Heating the film at 300 oC in Se-vapor converts this film to
5
6 SnSe2, as seen in Figure 3f), with the XRD peaks closely matching that of PDF 89-2939 of SnSe2 in
7
2θ positions and approximately in relative intensity. The crystalline grain size has by now dropped to
8
9 10 nm. In our previous work [6], we presented a survey of different ways of producing SnSe2 thin

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10 films. The SnSe2 film formed here would revert to SnSe only at temperatures near 500 oC. SnSe is
11
12 of p-type electrical conductivity, and SnSe2 formed from it is n-type, thereby offering the possibility to
13 form p-n thermoelectric junctions.
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17 3.3. Optical properties
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19
20
21 PbSe thin films: Figure 4 a) and b) show the optical specular reflectance (R) and transmittance (T) of
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PbSe thin films (600 nm), as-prepared (i) and after having heated at 300 oC (ii) and heated in presence
of Se-vapor (iii). The averaged optical reflectance at long wavelength for film (iii) is nearly 40 % (R =
0.4), which gives an estimate for refractive index [n = (1 + R½)/(1 – R½)] of 4.44 and high frequency
relative permittivity (εr = n2) of 20 at wavelength 2000 – 2500 nm. Reported value for epitaxial films of
PbSe at a wavelength 5000 nm is R = 0.435 and n = 4.88 [27]; and value for εr is 22.9. The static
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relative permittivity εro is 210 for bulk PbSe with Eg of 0.27 eV at room temperature [28]. The R and T
30
31 values help evaluate the optical absorption coefficient (α) for film of thickness d, by considering
32 multiple reflection inside the film [29]: α = (1/d)ln[(1 – R)2e-αd/(1 – R2e-2αd)], which are plotted against
33
34 photon energy (hν) in Figure 4 (c). Plots of (αhν)⅔ versus (hν) in Figure 4 d) and e) shows that the
35 electronic transitions are “forbidden type across a direct gap” [9]. Values of Eg are 1.14-1.5 eV for as-
36
37 prepared and heated films, and 0.77 eV after the film has been heated in Se-vapor. All these values
38 are above that of the bulk PbSe, arising from the quantum confinement expected from nano-crystals
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39
40 of 14-19 nm constituting these film. In chemically deposited PbSe thin films, but without preferential
41 orientation for (200) planes as here, Eg of 0.5 and 1 eV has been reported for crystallite diameters of
42
18 nm and 8 nm [24].
43
44
45 SnSe and SnSe2 thin films: In Figure 5 a) – e) is given the R, T, α, and (αhν)⅔ versus (hν) plots for
46 SnSe thin film (i), and after it had had been heated at 300 oC (ii) and for the film converted to SnSe2
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47
48 upon heating at 300 oC in Se-vapor (iii). Film (i) shows an indirect bandgap of 1.12 eV in Figure d), in
49 accordance with theoretical – experimental study [30]. Since this film maintains the orthorhombic
50
crystalline structure and crystalline diameter upon heating (Figure 3c), an increase in its Eg to 1.5 eV
51
52 upon heating seen in Figure 5 e) is unexpected, except that a minor component of SnSe 2 present in
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it makes the difference. For SnSe2 film, a bandgap of 1.5 eV falls within the reported values [6].
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3 3.4. Electrical conductivity
4

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5
6
7 Seebeck coefficient and the electrical conductivity are related through an inverse logarithmic
8 equation, which is approximately represented as [9]: S = 86 μV/K ln {[q(Nc or Nv)(μn or μp)/σ]}, where
9

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10 S will be negative for n-type and positive for p-type semiconductor. Higher is the σ of a semiconductor,
11 lower is its S. Having higher values of the carrier drift mobility μn or μp for n – or p – type
12
13 semiconductors helps, which are usually found in selenide and telluride chalcogenides of metals
14 compared with their sulfides. However, the electrical conductivity σ is the decisive parameter. Figure
15
6 a) – f) provides an overview of the electrical conductivity of the material of the films. A value of σ of
16

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17 6.5 - 11 Ω– 1 cm– 1 is available from p – PbSe in b) as well from n – SnSe2 in f). The best value from p
18 – SnSe in d) is 1 Ω– 1 cm– 1, even after heating at 300 oC. Since a range of electrical conductivities
19
20 may be acceptable for novel thermoelectric applications of semiconductors the screening criteria may
21 be left open. Avoiding toxicity in thermoelectric materials is a screening criterion, which would put p-
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SnSe/n-SnSe2 couples ahead of p-PbSe/n-SnSe2.

given a qualitative explanation:

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The changes in the electrical conductivity of the SnSe, and PbSe thin films upon heating may be
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Behavior of p-SnSe film upon heating in Se is its conversion to another material, n-SnSe2. The p-type
29
30 electrical conductivity of SnSe is due to Se-excess at ppm level compared with Sn, while n-type
31 electrical conductivity of SnSe2 may be due to interstitial or on-site Sn-excess. In either material,
32
33 vacancies of both elements exist in order to lower the free energy; the relative abundance of
34 vacancies at one site compared with the other is decisive in the conductivity type. Now, what happens
35
when a p-SnSe film is heated at 300 oC at 30 Torr nitrogen atmosphere without such Se-vapor? There
36
37 is a relative loss of Se from the sample, but excess of elemental Se that may exist in the sample
38 would become available and would compensate such loss. Hence the electrical conductivity may
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39
40 increase, even though crystalline grains have not grown (seen in XRD). This would not be the case
41 if the pressure is lowered to 300 mTorr - the electrical conductivity would decrease after heating at
42
43 300 oC. Incorporation of elemental Se in the SnSe film occurs because atmospheric oxygen (O2) in
44 contact with the solution can acquire electrons from selenide ions (S2-) and become (O2)2- thus making
45
elemental-Se available to the growing film in addition to selenide. Chemically deposited SnSe films
46
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47 have generally a Se-excess (Sn:Se of 40:60). Further discussion on this is available in ref [6].
48
49 Electrical conductivity of PbSe thin films prepared by the present solution composition (SSS + TU)
50
are orders of magnitude higher when deposited at higher temperature, 60 oC, but the films become
51
52 porous if thicknesses are allowed beyond 120 nm. However, the nucleation phase is not favored if
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the deposition is made at 30 oC – the resulting films are island-like, discontinuous and powdery. Thus,
54
55 the experimental approach in the present work was to deposit a PbSe thin film of 40-50 nm in
56 thickness at 60 oC, followed by deposition at 30 oC producing PbSe thin films of 400 nm (in 9 h) or
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3 600 nm (19 h). Hence a PbSe thin film of 400 nm in thickness has an underlying film of 40-50 nm of
4

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much higher electrical conductivity (due to on site Se-excess relative to on-site Pb). Heating the film
5
6 at 300 oC can make such excess evenly available, and the electrical conductivity of the film is retained
7
(Fig. 6a and Table 1) even if some loss of Se occurs due to the vacuum environment (20 mTorr). For
8
9 the film of higher thickness (600 nm), the Se-excess in the underlying film of 40-50 nm in thickness

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10 may not be sufficient to avert the overall loss and hence the electrical conductivity drops. When the
11
12 heating is done in the presence of Se-vapor, the electrical conductivity increased substantially in both
13 PbSe films. Such PbSe films are considered prospective thermoelectric materials.
14
15
16

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17 3.5. Thermoelectric characteristics
18
19
20
21 The electrical conductivity of the PbSe, SnS and SnSe2 thin films presented in Figure 6 generally
22
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28
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bear a direct relevance to the Seebeck coefficient S = V/ΔT obtained for these films from their
thermoelectric characteristics given in Figure 7 a) and b). Post deposition thermal processing alters
σ, and so does S. Table 1 lists the summary of values of crystalline grain diameter, Eg, σ and S of the
films 1 – 5 of p – PbSe films, 6 and 7 of p – SnSe films, and 8 and 9 of n – SnSe2 films and the V/ΔT
values of thermoelectric devices formed from these films described in Figure 7 c). The increase in σ
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29
from 0.18 to 6.4 Ω– 1 cm– 1 of PbSe film (600 nm) upon heating in Se – vapor leads to a reduction in
30
31 from 0.55 to 0.275 mV/K, and similar is the case with PbSe film 400 nm in thickness. Values of S of
32 0.220 mV/K is typical for PbSe single crystals near 300 K, though at much higher σ [31]. The value
33
34 of σ increases from 0.3 to 0.9 Ω– 1 cm– 1 for SnSe film (180 nm) upon heating, and this leads to a
35 reduction in S from 0.30 to 0.20 mV/K. In SnSe2 film, decrease in σ from 11.2 to 0.3 Ω– 1 cm– 1
36
37 increases the value of S from 0.35 to 0.375 mV/K. In the case of 5-element devices, the best value
38 for V/ΔT of nearly 2.5 mV/K is observed for 3 – 8 and 1 – 8 combinations, but the series resistance is
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39
least (50 kΩ) for 4 – 8 couples formed from p- and n- materials of best σ, 6 – 11 Ω– 1 cm– 1. These
40
41 resistances are high for conventional applications, but may be suitable for novel designs in which
42
fibers or foils coated with these semiconductors may be stacked to give same S at considerably lower
43
44 resistance across the ends.
45
46
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48 3.6. Thermoelectric prospects of chemically deposited PbSe, SnSe and SnSe2 thin films
49
50 Substrates: Thermoelectric elements are usually made from single crystals, and doping of the same
51
52 material to n- or p- type electrical conductivity is desired in conventional approach. Higher electrical
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53 conductivity and lower thermal conductivity of the material is desirable, which in general is hard to
54
achieve [8]. New outlook on the prospects of thermoelectric for widespread applications opens up
55
56 opportunities for a range of substrates as fibers or foils on which semiconductor coatings may be
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3 applied by chemical deposition. Polyimide [32] and polyether sulfone [33] foils have been reported to
4

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withstand postdeposition thermal processing of chemically deposited copper sulfide thin films at
5
6 temperatures of 300 oC, as employed here. In such composite media, the thermal conductivity of the
7
thermoelectric film would be higher than that of the substrate and new selection criteria must evolve.
8
9 For this reason, we have not endeavored to evaluate the dimensionless ZT of the materials for

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10 comparison. Series resistance of many kΩ, listed for the devices in Table 1, may be brought down by
11
12 stacking the coated and processed fibers or foils.
13
14 Relevance of optical properties in thermoelectric applications: Absorbed radiation A = 1 – (T + R),
15 which in the case of solar radiation can be nearly 50 % (of 1000 W/m 2) in the films in Figures 4a), b)
16

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17 and 5a) and b). Such optical absorption can heat up the exposed part of the film and leave the shaded
18 part cold, bringing-in temperature differential across the film (or stack of films). Since films (ii), and
19
20 (iii) in both cases have been subjected to heating up to 300 oC, these films are expected to remain
21 stable under sunlight at moderately elevated temperatures, 150 oC, at the hot end. Thermoelectric
22
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28
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effect in semiconductors is now being inducted into making innovative wearable and self-powered
thermoelectric devices powering other devices [4, 11], and hence is surpassing its conventional role
to provide thermoelectric cooling, heating or power generation using PbTe or Bi2Te3 p-n elements [4,
8]. Optical properties of the PbSe, SnSe, and SnSe 2 films discussed above becomes relevant to
dM
assess their suitability in novel thermoelectric devices, which may be forthcoming. Low thermal power
29
30 density sources at less than 100 W/cm 2 for generation or cooling are abundant in electronic devices
31 or in the nature [34].
32
33 Cost, toxicity and optimization: For large scale production of thermoelectric elements, cost has the
34
35 primary consideration. According to USGS Mineral Commodity Summary reports for 2016, world
36 production (and cost us$ per kg) of lead, tin, Se and Te were [35]: above 4.8 million tons ($2), 280,000
37
tons ($20), 2,200 tons ($45 – 70), and 400 tons ($35) respectively, with a price-drop in Te reported
38
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39 during 2016 as most drastic. Recovery of Se has been neglected in many mining sites for zinc, copper
40 and lead due to economic factors. Irrespective of price-drop, world reserve of Te is mentioned as
41
42 25,000 tons. Overall, the availability and cost are good for Pb, Sn, and Se to support any large scale
43 development of thermoelectric devices. In large-area large scale applications of lead chalcogenide
44
45 films, toxicity of lead compounds during preparation and their use should be assessed. We have
46 previously reported these aspects in the context of solar control application of PbS thin films produced
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47
in a closely similar way [36, 37] as for PbSe films in the present study. Our conclusion was that risks
48
49 are minimal when these films are prepared from aqueous solutions [35]. Optimization of the bath
50
composition for PbSe thin films has not been arrived at in this study. In the deposition solution for
51
52 PbSe, the ratio of Pb2+: sulfide/selenide was nearly four (7.25/1.7), which can be reduced toward one
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53 as for PbS films [37]. That will be a future task.

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3 Beyond this work: In this study we illustrated the characteristics of p-n-p-n-p thermoelectric devices
4

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prepared from p-PbSe, p-SnSe and n-SnSe2 thin films. Other thin films compatible with thermoelectric
5
6 applications, with electrical conductivity of 10 – 103 Ω–1 cm–1, which may be produced by chemical
7
deposition and made stable at 300 oC through thermal processing in nitrogen ambient include n-Bi2S3
8
9 [37], n-Bi2Se3 [38] and p-Cu2Se [39]. They have been originally evaluated in the context of

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10 photovoltaic applications in the 1990’s. Thin film p-Cu2Se has been found particularly stable [39]. By
11
12 itself, this material with σ of 330 Ω-1 cm-1, κ, 1 W m-1 K-1 and S, 0.16 mV/K at 600 K has a ZT of 0.5,
13 as seen a 2015 survey [40], but has been reported with ZT of 1.6 in 2012 and close to 2.6 in Cu2Se:Al
14
15 in 2014. In this way, it is at par with the ZT of SnSe of orthorhombic structure [4, 5]. Overall, many
16 materials which have been investigated in the past for photovoltaics, but had been sidelined because

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17
of their high electrical conductivity in a photovoltaic absorber role, can be used to form n-p couples
18
19 with matching internal resistance of its constituent thermoelectric components in stacks of coated
20
foils, fibers or composites. New outlook in thermoelectrics [4] offers prospects for them.
21
22
23
24
25
26
27
28
4. Conclusions an
We presented the chemical deposition of PbSe and SnSe thin films, and their post deposition thermal
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29 processing in Se-vapor which can change electrical conductivity of p-PbSe films and convert p-SnSe
30
31 films to n-SnSe2 films. This allows for designing different combinations of n-p thermocouples between
32 p-PbSe/n-SnSe2, and p-SnSe/n-SnSe2 with thermoelectric potential of up to 1 mV/K per couple.
33
34 Heating of the films at 300 oC is expected to lead to stable operation of the devices over many years.
35 The relevance of the results may be in conceiving novel thermoelectric applications. We suggested
36
the scope of chemically deposited thin films for technology development of various previously
37
38 reported materials for photovoltaics to be directed toward thermoelectrics.
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40
41
42 Acknowledgments
43
44 José Campos recorded SEM-EDS spectra; Patricia E Altuzar recorded the XRD patterns;
45
Yareli Colin Garcia assisted in the optical measurements; Luis Alberto Rodriguez helped in the initial
46
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47 work; Oscar Gomez Daza provided overall experimental support. Financial support was provided
48 from PAPIIT-UNAM IT100917 and CeMIE-Sol Project 35; infrastructure support was available from
49
50 CONACYT-LIFYCS 123122.
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1
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3 References
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5 [1] Zingaro R A, Skovlin D O 1964 Chemical deposition of thin films of lead selenide J. Electrochem.
6 Soc. 111 42-47
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[2] Nair G, Liang-Yi Chang, Geyer S M and Bawendi M G 2011 Perspective on the Prospects of a
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Carrier Multiplication Nanocrystal Solar Cell ACS Nano Lett. 11 2145–2151
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10 [3] Calixto-Rodriguez M, Moreno-García H, Nair M T S and Nair P K 2013 Antimony chalcogenide/lead
11 selenide thin film solar cell with 2.5% conversion efficiency prepared by chemical deposition, ECS J.
12 Solid State Sci. Technol. 2 Q69-Q73
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14 [4] Rojas J P, Singh D, Inayat S B, Torres-Sevilla G A, Fahad H M and Hussain M M 2017 Review—
15 Micro and Nano-engineering enabled new generation of thermoelectric generator devices and
16 applications, ECS J. Solid State Sci.Technol. 6 N3036-N3044

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18 [5] Zhao LD, Lo S H, Zhang Y, Sun H, Tan G, Uher C, Wolverton C, Dravid V P and Kanatzidis M G
19 2014 Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals Nature
20 508 373–377
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22 [6] Barrios-Salgado E, Nair M T S and Nair P K 2016 Thin films of n-type SnSe2 produced from chemically
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deposited p-type SnSe Thin Solid Films 598 149–155

[7] O'Dwyer C, Chen R, Jr-Hau He and Lee J, Kafil M R 2017 Preface—Focus Issue on
Thermoelectric Materials & Devices: Phonon Engineering, Advanced Materials and Thermal
Transport, ECS J. Solid State Sci. Technol 6(3): Y3; doi:10.1149/2.0161703jss
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[8] Sorensen H A 1983 Energy Conversion Systems John Wiley New York 425
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30 [9] Smith R A, Semiconductors 1978 2nd ed. Cambridge University 153
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32 [10] Sze S M Physics of Semiconductor Devices 1981 Second ed. Wiley New York 850
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34 [11] Caballero-Caleroa O and D’Agosta R 2017 Review — Towards the next generation of
35 thermoelectric materials: tailoring electronic and phononic properties of nanomaterials ECS J. Solid
36 State Sci. Technol. 6 N3065-N3079
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38 [12] Wadia C, Alivisatos A P, Kammen D M 2009 Materials availability expands the opportunity for
large-scale photovoltaics deployment Environ. Sci. Technol. 43 2072
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40 [13] Repins I L, Romero M J, Li J V, Su-Huai Wei, Kuciauskas D, Jiang C S, Beall C, De Hart C, Mann
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[15] Skelton J M, Burton L A, Jackson A J, Oba F, Parkera S C and Walsh A 2017 Lattice dynamics
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of the tin sulphides SnS2, SnS and Sn2S3: Vibrational spectra and thermal transport Phys. Chem.
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51 [16] Barrios-Salgado E, Rodríguez-Guadarrama L A, Garcia-Angelmo A R, Álvarez J C, Nair M T S
52 and Nair P K 2016 Large cubic tin sulfide – tin selenide thin film stacks for energy conversion Thin
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3 [17] Liu H and Chang L L Y 1992 Phase relations in systems of tin chalcogenides J. Alloys and
4 Compounds 185 183-190

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6 [18] Barrios-Salgado E, Nair M T S and Nair P K 2014 Chemically deposited SnSe thin films: thermal
7 stability and solar cell application ECS J. Solid State Sci. Technol. 3 Q169-Q175
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9 [19] Fafanov G M, Kitaev G A 1969 Analysis of the conditions for the precipitation of metal selenides

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10 from aqueous solutions with sodium selenosulphate Russ. J. Inorganic Chem. 14 322-324
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12 [20] Hodes G 2003 Chemical solution deposition of semiconductor films Marcel Dekker New York 56
13 [21] Bindu K and Nair P K 2004 Semiconducting tin selenide thin films prepared by heating Se-Sn
14 layers Semicond. Sci. Technol. 19 1348-1353
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16 [22] Bindu K, Nair M T S and Nair P K 2006 Chemically deposited Se thin films and its use as a planar

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17 source of selenium for the formation of metal selenide layers J. Electrochem. Soc 153 C526-C534
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19 [23] Nair P K, Barrios-Salgado E, Capistrán J, Ramón M L, Nair M T S and Zingaro R A 2010 PbSe thin
20 films in all-chemically deposited solar cells J. Electrochem Soc. 157 D528-D537
21
22 [24] Gorer S, Albu-Yaron A and Hades G 1995 Quantum size effects in chemically deposited
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nanocrystalline lead selenide films J. Phys. Chem. 99 16442-16448

[25] Barrios-Salgado E, Nair M T S, Nair P K and Zingaro R A 2011 Chemically deposited thin films
of PbSe as an absorber component in solar cell structures Thin Solid Films 519 7432–7437

[26] Pramanik P and Bhattacharya S 1988 A chemical method for the deposition of tin(II) selenide
thin films J. Mater. Sci. Lett. 7 1305-1306
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30 [28] Amirtharaj P M and Seiler D G in Handbook of Optics Volume II Chapter 36 Optical Properties
31 of Semiconductors University of Gent accessed on 03 Nov. 2017: http://
32 www.photonics.intec.ugent.be/education/ivpv/res_handbook/v2ch36.pdf
33
[29] Pankove J I 1975 Optical Processes in Semiconductors Dover New York
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35 [30] Parenteau M and Carlone C 1990 Influence of temperature and pressure on the electronic
36 transitions in SnS and SnSe semiconductors Phys. Rev. B 41 5277-5234
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38 [31] Kogo G, Pradhan A K and Roy U N 2017 Thermoelectric behavior of PbSe single crystals ECS
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39 J. Solid State Sci. and Technol. 6 N3006-N3009

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41 [32] Cardoso J, Gomezdaza O, Ixtlilco L, Nair M T S and Nair P K 2001 Conductive copper sulfide thin
42 films on polyimide foils Semicond. Sci. Technol. 16 123-127
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44 [33] Nair P K, Cardoso J, GomezDaza O and Nair M T S 2001 Polyethersulfone foils as stable transparent
45 substrates for conductive copper sulfide thin film coatings Thin Solid Films 401 243-250
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47 thermal transport and thermoelectric materials and devices ECS J. Solid State Sci. Technol. 6 N3058-
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50 [35] United States Geological Survey (USGS) Mineral Commodity Summary Reports accessed on
51 02 Nov. 2017 https://minerals.usgs.gov/minerals/pubs/commodity/lead/mcs-2017-lead.pdf;
52 https://minerals.usgs.gov/minerals/pubs/commodity/tin/mcs-2017-tin.pdf;
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53 https://minerals.usgs.gov/minerals/pubs/mcs/2017/mcs2017.pdf
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55 [36] Nair P K, Nair M T S, Fernandez A M and Ocampo M 1989 Prospects of chemically deposited metal
56 chalcogenide thin films as solar control coatings, J. Phys D – Appl. Phys. 22 829-836
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3 [37] Nair P K and Nair M T S 1990 PbS solar control coatings: safety cost and optimization J. Phys.
4 D – Appl Phys. 23 150-155

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6 [38] Nair P K, Campos J, Sanchez A, Baños L and Nair M T S 1991 Amorphous-crystalline trans-
7 formation and conductivity enhancement in annealed bismuth sulfide thin films Semicond. Sci. Technol.
8 6 393-396
9

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10 [39] García V M, Nair M T S, Nair P K and Zingaro R A 1997 Chemical deposition of bismuth selenide
11 thin films using N,N-dimethylselenourea Semicond. Sci. Technol. 12 645-653
12 [40] Zhang X and Zhao L D 2015 Thermoelectric materials: Energy conversion between heat and
13 electricity J. Materiomics 1 92-105
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5
6 Table 1 Summary of parameters of PbSe, SnSe and SnSe2 films as prepared, and heated at 300 oC:
7
Grain diameter (D) from XRD patterns of Figures 2 and 3; bandgap (E g) from Figures 4 and 5;
8
9 electrical conductivity (σ) from Figure 6 and Seebeck coefficient S from Figure 7 with Sample number

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10 following that in Figure 7. Thermoelectric parameters of 5 element devices are in last three rows.
11
12
13 Sample D (nm) Eg (eV) σ (Ω– 1 cm– 1) S (mV/K)
14 1 PbSe 600 nm 15 1.17 0.18 0.512
15 2 PbSe 400 nm 12 - 0.14 0.457
16

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3 PbSe 400 nm 300 oC – Se 16 - 6.1 0.295
17
18 4 PbSe 600 nm 300 oC – Se 18.7 0.77 6.4 0.262
19 5 PbSe 600 nm 300 oC 14.7 1.14 0.003 0.118
20 6 SnSe 180 nm 19 1.12 0.3 0.295
21 7 SnSe 180 nm 300 oC 18 1.5 0.9 0.186
22
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8 SnSe2180(+5)nm(300 oC)
9 SnSe290(+10)nm(300 oC)
Device p – n – p – n – p
V/ΔT (mV/K)
Series resistance (Ω)
10
-

2.38
55 k
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3 PbSe/8 SnSe2
1.5
-
1 PbSe/8 SnSe2
2.37
540 k
11.2
0.3
4 PbSe/8 SnSe2
1.39
50 k
0.297
0.351
7 SnSe/8 SnSe2
0.79
177 k
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3 Figure Captions
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5 Figure 1 a) Energy dispersive X-ray spectral emission lines from PbSe thin film of 600 nm in thickness,
6
as prepared (bottom) and heated; and b) of SnSe thin film of 180 nm in thickness as prepared (bottom)
7
8 and SnSe2 film of 185 nm thickness produced from it.
9

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11 Figure 2 a) Powder diffraction file of PbSe, showing the (hkl) values and relative intensities of the
12 diffraction peaks; b) GIXRD recorded at grazing incidence 2.5 o for as-prepared PbSe film of 600 nm
13
14 in thickness; c) zoom-in on the (200) peak of the as-prepared film with crystalline diameter 15 nm,
15 heated at 300 oC with 14.7 nm, and heated in Se-vapor with 18.7 nm; d) log plot of the relative intensity
16

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of data b) illustrating the presence of all-odd, all-even (hkl) combinations for rock-salt structure, with
17
18 texture coefficient (TC) of 3.2 for (200) diffraction; e) for the film heated at 300 oC with TC of 3.8 for
19 (200); and f) for the film heated in Se-vapor with TC of 3.9.
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an
Figure 3 a) Powder diffraction file 89-0232 for SnSe – orthorhombic, which a good match for the
GIXRD pattern for SnSe thin film of b), with a crystalline grain diameter of 19 nm determined from
(111) peak shown in the inset; c) heating the film at 300 oC leaves the XRD pattern and grain diameter
(18 nm, inset) nearly intact except that a minor peak of SnSe2 at 2θ = 14.42o shows up; d) Log-scale
intensity plot showing that all other peaks belong to SnSe – orth; e) PDF 89-2939 for SnSe2 is a good
dM
29
match for the SnSe2 film produced at 300 oC in Se-vapor in f) with grain diameter 10 nm (inset).
30
31
Figure 4 a) Optical reflectance (R); b) Optical transmittance (T); c) Optical absorption coefficient (α);
32
33 and (αhν)⅔ versus photon energy (hν) plots for: d) as prepared (i), and heated (ii) PbSe thin films and
34
e) for the film (iii) heated in Se-vapor at 300 oC.
35
36
Figure 5 a) Optical reflectance (R); b) Optical transmittance (T); c) Optical absorption coefficient (α);
37
38 d) (αhν)½ versus photon energy (hν) plots for SnSe film (i); and e) (αhν)⅔ versus photon energy (hν)
pte

39
plots for heated SnSe film (ii) and that was converted to SnSe 2 (iii) by heating in Se-vapor.
40
41
Figure 6 Electrical conductivity of: a) p – type PbSe films of thickness 400 nm and 600 nm, as
42
43 prepared, heated at 300 oC and heated at 300 oC in Se – vapor; b) Photoconductivity rise and decay
44 in the film 600 nm 300 oC-Se; c) p – type SnSe films of thickness 90 nm and 180 nm, as prepared
45
46 and heated at 300 oC; d) Photoconductivity rise and decay in the film 180 nm 300 oC; e) n-type SnSe2
ce

47 of 100 and 185 nm in thickness produced by heating in Se the SnSe films; f) Photoconductivity rise
48
49 and decay in SnSe2 film 185 nm in thickness.
50
51 Figure 7 Thermoelectric potential (V) versus differential temperature ΔT in room temperature interval:
52 a) p – PbSe thin films of 400 and 600 nm in thickness, as prepared and subjected to heating as
Ac

53
54 specified with S = V/ΔT values listed in Table 1; b) p – SnSe and n – SnSe2 films; c) of p-n-p-n-p five-
55 element thin film thermocouples (scheme in the insets) formed from materials 1 – 9 of a) and b).
56
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 AUTHOR SUBMITTED MANUSCRIPT - SST-104282.R1 Page 18 of 24

1
2
3
4

pt
5
6
7
8
9 4
a) b)

cri
Se
10 Se-L1,2 Pb-M1,2 Se-L1
Se-L 1.204
11 1.379 2.342 1.379 Se-L 1.245
12 8
Pb-M Na
13 Na-K1,2 1.041
2.44
14 3
15 Pb-M Pb-M
16
Intensity (u. a.)

us
Na Se 1.83 2.66
17 6
18 PbSe 300°C(Se) Sn-L1 Sn-L1
Si-K1,2
19 2
3.44 3.66
1.74
20
21 4
22
23
24
25
26
27
28
1
PbSe 300°C

S-K1,2
2.31
an 2
Na Se
SnSe2
dM
29 PbSe600nm
SnSe180nm
30 0 0
31
1 2 3 1 2 3 4
32
photon energy (keV)
33
34
35
36
37 Figure 1 a) Energy dispersive X-ray spectral emission lines from PbSe thin film of 600 nm in thickness,
38 as prepared (bottom) and heated; and b) of SnSe thin film of 180 nm in thickness as prepared (bottom)
pte

39 and SnSe2 film of 185 nm thickness produced from it.

40
41
42
43
44
45
46
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47
48
49
50
51
52
Ac

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Page 19 of 24 AUTHOR SUBMITTED MANUSCRIPT - SST-104282.R1

1
2
3
4 (hkl) 2 TC

pt
5 100 f) PbSe 300 °C (Se)
(111) 25.18 0.1
6 10
(200) 29.15 3.9
7
1 (220) 41.7 0.2
8
9 0.1 (311) 49.34 0.7

cri
10 (222) 51.69 0.1
0.01
11
12 100 e) PbSe 300 °C (hkl) 2 TC
13 (111) 25.18 0.2
14 10 (200) 29.15 3.8
15 (220) 41.7 0.2
16 1

us
(311) 49.34 0.7
17
Relative intensity

(222) 51.69 0.1

18 0.1
19
20 100 d) PbSe (hkl) 2 TC
21 600 nm (111) 25.18 0.6
22 10 (200) 29.15 3.2
23
24
25
26
27
1

0.1
an (220)
(311)
(222)
41.7
49.34
51.69
0.3
0.7
0.2

(200)
Intensity (104 cps)
28 b) PbSe 16 c)
dM
100 D (nm)
29 600 nm 18.7
12
30 14.7
8
31 50 15
32 4
33
0 0
34 28.5 29.0 29.5 30.0
35 100 a) PDF PbSe 78-1903 2 (deg)
36
(111)

(222)

(331)
(311)
(200)

(220)

(400)

(420)

37 50
100
37

66

21

21
15

5
8

38
0
pte

39
10 20 30 40 50 60 70
40
2 (deg)
41
42
43
44
45 Figure 2: a) Powder diffraction file of PbSe, showing the (hkl) values and relative intensities of the
46 diffraction peaks; b) GIXRD recorded at grazing incidence 2.5 o for as-prepared PbSe film of 600 nm
ce

47 in thickness; c) zoom-in on the (200) peak of the as-prepared film with crystalline diameter 15 nm,
48 heated at 300 oC with 14.7 nm, and heated in Se-vapor with 18.7 nm; d) log plot of the relative intensity
49 of data b) illustrating the presence of all-odd, all-even (hkl) combinations for rock-salt structure, with
50 texture coefficient (TC) of 3.2 for (200) diffraction; e) for the film heated at 300 oC with TC of 3.8 for
51 (200); and f) for the film heated in Se-vapor with TC of 3.9.
52
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 AUTHOR SUBMITTED MANUSCRIPT - SST-104282.R1 Page 20 of 24

1
2
3
4

pt
100 f) SnSe2-185 nm

Intensity (103 cps)

5
4 D=10 nm

6 300 °C

(011) SnSe2
2
7 50
8
0
9 30 31 32

cri
2 (deg)
10 0
11
100
12 e) PDF SnSe2 89-2939
13
50

(201)
(012)
(011)

(110)
(001)

(100)

(111)
14
15
0
16

us
17 100 d) SnSe-180 nm
18 300 °C
19 *
Relative intensity

20 10
21 * SnSe2 (001)
22 1
23
24
25
26
100 c) SnSe-180 nm
300 °C an Intensity (103 cps)
4
D=18 nm

(111) SnSe
27 50
2

28
dM
0
29 * 30 2 (deg) 31
30 0
31
100
Intensity (103 cps)

32 b) SnSe 4
D=19 nm
180 nm
33
(111) SnSe

34 50
2

35
36 0
30 31
37 0
2 (deg)

38
100
pte

39 a) PDF SnSe 89-0232

(400) (111)

40
(121)

(420)
(020)

(022)

50
(311)
(210)

(011)

41
42 0
43 10 20 30 40 50 60 70
44
2 (deg)
45
46
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47 Figure 3 a) Powder diffraction file 89-0232 for SnSe – orthorhombic, which a good match for the
48 GIXRD pattern for SnSe thin film of b), with a crystalline grain diameter of 19 nm determined from
49
(111) peak shown in the inset; c) heating the film at 300 oC leaves the XRD pattern and grain diameter
50
51 (18 nm, inset) nearly intact except that a minor peak of SnSe2 at 2θ = 14.42o shows up; d) Log-scale
52 intensity plot showing that all other peaks belong to SnSe – orth; e) PDF 89-2939 for SnSe2 is a good
Ac

53 match for the SnSe2 film produced at 300 oC in Se-vapor in f) with grain diameter 10 nm (inset).
54
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Page 21 of 24 AUTHOR SUBMITTED MANUSCRIPT - SST-104282.R1

1
2
3
4 100

pt
5 a) i) PbSe 600nm; ii) PbSe 300°C
6 iii) PbSe 300°C (Se)

R (%)
7
8 50
iii)
9

cri
ii)
10
i)
11 0
12 100 b)
13
T (%)

14 i)
15 50
16

us
ii)
17
18 iii)
0
19 500 1000 1500 2000 2500
20
21  (nm)
22
23
24
25
26
105

104
c)
an
(cm-1)

27
28 103
dM
29
30 iii) ii) i)
102
31
32 101
33
34
35 100
36 0.6 0.9 1.2 1.5 1.8 2.1 2.4 2.7
37 h (eV)
(h)2/3 (102 cm-2/3 eV2/3)

38 6 6
d)
pte

39
5 e)
40 ii) i) iii)
41 4 4
42
43 3
eV

V
eV

44
0.77 e

2 2
1.14

45
1.17

46 1
ce

47
48
0 0
49 1.0 1.2 1.4 0.6 0.8 1.0 1.2
h (eV)
50
51
52 Figure 4 a) Optical reflectance (R); b) Optical transmittance (T); c) Optical absorption coefficient (α);
Ac

53 and (αhν)⅔ versus photon energy (hν) plots for: d) as prepared (i), and heated (ii) PbSe thin films and
54 e) for the film (iii) heated in Se-vapor at 300 oC.
55
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1
2
3
4 100

pt
5 a) i) SnSe 180nm; ii) SnSe 300°C
6 iii) SnSe2 300°C

R (%)
7 ii)
50
8 iii)
9

cri
10 i)
11 0
100 b)
12
i)
13
T (%)

14 iii)
50
15
16 ii)

us
17
18 0
19 500 1000 1500 2000
20  (nm)
21
106
22 c)
23
24
25
10 5

an
(cm-1)

104
26
27 103
28
dM
29 102 i) ii) iii)
30
31 101
32
33 100
34 1.2 1.6 2.0 2.4 2.8 3.2 3.6 4.0
35 h (eV)
eV )

36 6 8
1/2

(h)2/3 (103 cm-2/3 eV2/3)

37 d) e)
38 6
-1/2

i) ii) iii)
pte

39 4
(10 cm

40
41
4
2

42 2
43 2
1/2
(h)

44 1.12 eV 1.5 eV
45 0 0
46 1.2 1.5 1.8 1.0 1.5 2.0 2.5
ce

47 h (eV)
48
49
Figure 5 a) Optical reflectance (R); b) Optical transmittance (T); c) Optical absorption coefficient (α);
50
51 d) (αhν)½ versus photon energy (hν) plots for SnSe film (i); and e) (αhν)⅔ versus photon energy (hν)
52 plots for heated SnSe film (ii) and that was converted to SnSe 2 (iii) by heating in Se-vapor.
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Page 23 of 24 AUTHOR SUBMITTED MANUSCRIPT - SST-104282.R1

1
2
3 11.4
4 10 e) n-SnSe2 f) SnSe2 185 nm

pt
5 (SnSe, 300°C-Se)
6
1 11.3
7
8
9 0.1

cri
10 11.2
11
0.01
12
100 nm 185 nm
13 11.1
14
15 10 c) p-SnSe 1 d) SnSe 300°C
16 180 nm

us
(-1 cm-1)

17 300°C
18 1
19 0.95
as prep.
20 0.1 300°C
21
22
23
24
25
26
27
28
0.01

10 a) p-PbSe
as prep.

90 nm

300°C-Se
an180 nm

300°C-Se
0.9

6.7
b) PbSe 600 nm
300°C-Se
dM
29 1
30 as prep. 6.6
as prep.
31 0.1 30 s 30 s 30 s
32 300°C dark photo dark

33 6.5
34 0.01 300°C
35 400 nm 600 nm
30 s
dark
30 s
photo
30 s
dark
6.4
36 0 30 60 90
0 30 60 90 120 150 180
37 time (s)
38
pte

39
40 Figure 6: Electrical conductivity of: a) p – type PbSe films of thickness 400 nm and 600 nm, as
41
prepared, heated at 300 oC and heated at 300 oC in Se – vapor; b) Photoconductivity rise and decay
42
in the film 600 nm 300 oC-Se; c) p – type SnSe films of thickness 90 nm and 180 nm, as prepared
43
44 and heated at 300 oC; d) Photoconductivity rise and decay in the film 180 nm 300 oC; e) n-type SnSe2
45 of 100 and 185 nm in thickness produced by heating in Se the SnSe films; f) Photoconductivity rise
46 and decay in SnSe2 film 185 nm in thickness.
ce

47
48
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 AUTHOR SUBMITTED MANUSCRIPT - SST-104282.R1 Page 24 of 24

1
2
3 20
4 a) 1 PbSe600 nm; 2 PbSe400nm

pt
3 PbSe400 nm 300°C-Se
5 15 T 4 PbSe600 nm 300°C-Se
6 5 PbSe600 nm 300°C 1
7 2
8 10
9 3

cri
10 5 4
11 5
12
13 0
10
14
b) 6 SnSe180 nm 6
15 7 SnSe180 nm 300°C
16 5 7

us
T
17
V (mV)

18
0
19
20
21 -5
22 8 SnSe2185 nm 8
23
24
25
26
27
28
-10

40
0

c) T
1
5

T2
-
9 SnSe2100 nm

10 15
an 20

3-8

1-8
9

25 30
dM
29 +
30 T=T2-T1
31 4-8
32 20
33
7-8
34
35 3-9
36
37 0
38 0 5 10 15 20
T (K)
pte

39
40
41 Figure 7 Thermoelectric potential (V) versus differential temperature ΔT in room temperature interval:
42 a) p – PbSe thin films of 400 and 600 nm in thickness, as prepared and subjected to heating as
43 specified with S = V/ΔT values listed in Table 1; b) p – SnSe and n – SnSe2 films; c) of p-n-p-n-p five-
44 element thin film thermocouples (scheme in the insets) formed from materials 1 – 9 of a) and b).
45
46
ce

47
48
49
50
51
52
Ac

53
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