Journal of Electronic Materials

Tetravalent Manganese-doped Lithium Meta-Silicate Red Emitting Phosphors for LEDs

Applications: Structural & Luminescence Properties
--Manuscript Draft--

Manuscript Number: JEMS-D-23-02170

Full Title: Tetravalent Manganese-doped Lithium Meta-Silicate Red Emitting Phosphors for LEDs
Applications: Structural & Luminescence Properties

Article Type: Original Research

Keywords: Li2SiO3:xMn4+, Photoluminescence; Red-emitting phosphors, Raman spectra

Abstract: In this paper, different concentartion of tetravalent Manganese activated Lithium meta-
silicate red emitting phosphors namely Li2SiO3:xMn4+ has been prepared by solid
state reaction method at 950°C for 3 hours. The structural, thermal, morphology and
optical properties of the phosphor are characerized by PXRD, TGA/DSC, SEM/EDX,
FTIR, Raman, UV-Visible and PL spectra were investigated in detail. Excitation and
emission spectra are used to study optical characteristics. which matches well with the
commercial visible region and red emission bands peaking at around 642 nm for
Li2SiO3:0.02Mn4+ and peaking at around 717 nm for Li2SiO3:0.02Mn4+ by the 2E
→4A2 transition. The optimal doping concentrations of Li2SiO3:xMn4+ were studied
through the relationships between the Mn4+ doping concentration and luminescence
intensity. The Commission Internationale de l'Eclairage (CIE) chromatic coordinate
graph confirmed the emission color observation, which was in the red region and
showed an excellent color purity. In addition, the quantum efficiency
Li2SiO3:Mn4+phosphors reached up to 70.51%. The investigation shows that
synthesized Li2SiO3:Mn4+phosphors are beneficial for red LEDs used in solid state
lighting.

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Cover letter Click here to access/download;Cover letter;Cover letter.docx

To,

The Editor in Chief

Journal of Electronic Materials

Subject: Submission of manuscript for evaluation and publication.

I am herewith sending you a manuscript proposed entitled: “Tetravalent Manganese-

doped Lithium Meta-Silicate Red Emitting Phosphors for LEDs Applications:

Structural & Luminescence Properties by Priya Barik, Ishwar Prasad Sahu, Aksh

Kumar Verma, Anjali Mehto for its kind evaluation and publication in your esteemed

journal. With the submission of this manuscript, I would like to undertake that the above-

mentioned manuscript is our original work, which has neither published anywhere nor

accepted for publication anywhere or under editorial review for publication. I hope that the

findings of this paper will serve as a guide to the experimental scientists for future

investigations.

Look forward to hear your kind response.

With Regards

Ishwar Prasad Sahu

 Click here to access/download;Manuscript;journal of electronic
material-Mn.docx
Click here to view linked References

1
Tetravalent Manganese-doped Lithium Meta-Silicate Red Emitting Phosphors
2
3 for LEDs Applications: Structural & Luminescence Properties
4
5
1Priya Barik, 1Ishwar Prasad Sahu* 2Aksh Kumar Verma, 3Anjali Mehto
6
7
8
9 1
Department of Physics, Indira Gandhi National Tribal University, Amarkantak 484887,
10
11 Madhya Pradesh, India
12
2
13 School of Studies in Physics and Astrophysics, Pt. Ravishankar Shukla University, Raipur,
14
15 492010 Chhattisgarh, India
16 3
17
Department of Physics, Dr. Hari Singh. Gour Vishwavidyalaya Sagar, Madhya Pradesh
18 470003, India
19
20
21 *Corresponding author Email Id: ishwarprasad1986@gmail.com
22
23
24 Abstract
25
26
27
28 In this paper, different concentartion of tetravalent Manganese activated Lithium
29
30 meta-silicate red emitting phosphors namely Li2SiO3:xMn4+ has been prepared by solid state
31
32
33 reaction method at 950℃ for 3 hours. The structural, thermal, morphology and optical
34
35 properties of the phosphor are characerized by PXRD, TGA/DSC, SEM/EDX, FTIR, Raman,
36
37
UV-Visible and PL spectra were investigated in detail. Excitation and emission spectra are
38
39
40 used to study optical characteristics. which matches well with the commercial visible region
41
42 and red emission bands peaking at around 642 nm for Li2SiO3:0.02Mn4+ and peaking at
43
44
45 around 717 nm for Li2SiO3:0.02Mn4+ by the 2E → 4A2 transition. The optimal doping
46
47 concentrations of Li2SiO3:xMn4+ were studied through the relationships between the Mn4+
48
49
50 doping concentration and luminescence intensity. The Commission Internationale de
51
52 l'Eclairage (CIE) chromatic coordinate graph confirmed the emission color observation,
53
54
55
which was in the red region and showed an excellent color purity. In addition, the quantum
56
57 efficiency Li2SiO3:Mn4+phosphors reached up to 70.51%. The investigation shows that
58
59 synthesized Li2SiO3:Mn4+phosphors are beneficial for red LEDs used in solid state lighting.
60
61
62 1|Page
63
64
65
 1
2 Keywords: Li2SiO3:xMn4+, Photoluminescence; Red-emitting phosphors, Raman spectra.
3
4
5
6 1 Introduction
7
8
9 The development of rare earth (RE) ions activated red-emitting phosphors, including
10
11 Eu3+, Tb3+, Sm3+, and Pr3+, has received a lot of attention in recent years. [1-6]. notably, its
12
13
14 broad use is constrained by the high cost of the rare earth ions required. Non-rare earth
15
16 (NRE) based environment phosphors have garnered a lot of attention due to the need to lower
17
18
19 the cost of the ligth emitting diodes (LED) equipment and the soaring costs of RE ions[7].
20
21 Due to its deep-red emission wavelength, the NRE Mn4+ ion is currently the subject of
22
23
24
extensive research for white LEDs used in general illumination applications[8]. One of the
25
26 biggest challenges in the field of luminescent materials is developing new red phosphors,
27
28 especially when red-emitting phosphors are preferred in certain situations due to their high
29
30
31 colour purity and deep-red photoluminescence (PL) quality. As a result, these phosphors are
32
33 widely used to enhance the colour rendering property and increase the efficacy of W-LEDs.
34
35
36 [9,10]. As a result, the ideal red phosphor should have a mix of characteristics including easy
37
38 synthesis, low cost, a relatively wide absorption band, and good luminescence efficiency[11].
39
40
41 Due to their high efficiancy and restricted emission band, RE ions, particularly Eu3+
42
43
44 ions, have received a lot of attention[12-14]. Mn4+ ions, as a NRE, has 3d3 electron
45
46 configuration can show strong absorption from the near-ultraviolet (NUV) to blue region and
47
48
49 emit red or deep red emission in the region from 600 to 780 nm in different crystal field
50
51 environment [15-18]. Different types of Mn4+-activated oxide hosts, including as aluminates,
52
53
54 germinates, silicates, perovskites, double perovskites, and more, have been reported[19-24].
55
56 However, over the last few years, a significant number of unique Mn4+-activated red emitting
57
58
59
fluorides or oxides phosphors have been developed[8]. In comparison to fuorides, more
60
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62 2|Page
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65
 chemically stable oxide phosphors have longer Mn4+ emission wavelengths[25]. Here, we
1
2 classified Mn4+-activated phosphors such as(Sr3Al10SiO20:Mn4+, CaMgAl10O17,
3
4
5 K2TiF6:Mn4+, K2(Ge0.999Mn0.001)4O9, Rb2(Ge0.999Mn0.001)4O9, CaZrO3:Mn,
6
7 Y2Mg3Ge3O12:Mn4+,Li+) [26-32]. When Mn4+ resides in an octahedral site, it typically
8
9
10 exhibits strong and broad absorption spanning the wavelengths of 300 to 480 nm and bright
11
12 line emission between 600 and 760 nm. With regard to these merits and as the spectroscopic
13
14
15 properties almost ideally match the requirements, Mn4+ is a promising activator for red
16
17 phosphors in warm WLEDs[33-35]. Additionally, as far as we are aware, there has never
18
19
20
been any reported on the Li2SiO3:Mn4+ phosphors.
21
22
23 In this work, a red phosphor Li2SiO3:xMn4+ is synthesized by solid-state reaction
24
25 method in air and to describe their structural, thermal properties, morphological and
26
27
28 luminescence properties by means of Powder X-ray diffractometry (PXRD), Differential
29
30 Scannning Calorimetry (DSC), Thermogravimetric (TGA), Scanning Electron Microscopy
31
32
33 (SEM), Fourier Transform Infrared spectroscopy (FTIR), UV-Visible and PL spectra. A
34
35 comparative research was conducted on the excitation and emission spectra, and fluorescence
36
37 lifetime, of Mn4+ in the Li2SiO3:xMn4+ (excitated by both 425 and 475 nm) were measured.
38
39
40 The luminous mechanism is explained by Tanabe-Sugano energy level diagram.
41
42
43 2. Experimental
44
45
46
47
2.1 Phosphors Synthesis Methods
48
49
50 A series of Li2SiO3: xMn4+ (x= 0.01, 0.02, 0.03, 0.04, and 0.05mol) phosphors were
51
52 prepared via a solid-state reaction method in air atmosphere. Li2CO3 (99.90%), SiO2
53
54
55 (99.95%), and high purity MnO2 (99.99%) (Make - HIMEDIA). The following chemical
56
57 reaction were used for stoichiometric equation balance of host and with Mn doping.
58
59
60
61
62 3|Page
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64
65
 Li2 CO3 + SiO2 → Li2 SiO3 + CO2 (1)
1
2
3 Li2 CO3 + SiO2 + xMnO2 → Li2 SiO3 : xMn4+ + CO2 + O2 (2)
4
5
6
7 After cooling the final products to room temperature, the resulting powder was
8
9 subsequently cushed once more and employed for additional characterization.
10
11
12
13
2.2 Phosphors Characterization Techniques
14
15
16 The sample crystal structure and phase formation were determined using the
17
18 PANalytical 3kW X'pert powder XRD. Utilising monochromatic Cu-Kα radiation
19
20
21 (λ=1.54060) at 40 kV and 100 mA, we were able to obtain the diffraction pattern. The
22
23 acquired PXRD patterns were then compared to file no. 29-829 of the standard joint
24
25
26
committee on powder diffraction standards (JCPDS). In a step-scanning mode, data for the
27
28 Rietveld analysis were gathered in the scattering angle range (2θ) from 10o to 80o with a
29
30 scanning step of 0.01o. Using the Full Prof programme, Rietveld refinement was carried out.
31
32
33 The peak shapes used in the calculations were of the pseudo-voigt variety. For the analysis of
34
35 thermal behavior using thermo-gravimetric (TGA), STARE SYSTEM, TGA1 SF/1100,
36
37
38 METTLER. TGA study was performed in flowing N2 (70.00ml/min) from 25oC to 1000oC
39
40 with heating rate of 20 K/min. The well mixed reactants are placed at alumina crucible. The
41
42
43 SEM Model-EVO 18 was used for imaging of surface morphology of the prepared sample
44
45 and the elemental (qualitative & quantitative) analysis was also investigated by the Energy
46
47
dispersive X-ray Spectroscopy (EDX). Using Fourier Transform Infrared Spectroscopy
48
49
50 (FTIR), Alpha-II ECO ATR, BRUKER, and the combination, composition, purity,
51
52 vibrational characteristics, and other impurities of all of the functional groups of synthesised
53
54
55 compounds were observed. Raman spectra recorded by Technos STR-500 micro-Raman
56
57 spectrometer equipped with 500 nm (green laser). UV-vis spectra are measured by using a
58
59
60 Shimadzu UV-3600 spectrometer at room temperature. Using a fluoro max-4cp_1715D-
61
62 4|Page
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65
 2218-FM equipped with a 150 W ozone-free Xenon arc lamp as the excitation light source,
1
2 the excitation and emission spectra with lifetime were measured. The CIE 1931 colour
3
4
5 coordinate system was converted from the samples' PL emission spectra, and the colour
6
7 coordinates corresponding to the predominant emission were found. All the measurements
8
9
10 were recorded at room temperature.
11
12 3. Result and Discussion
13
14
15
16
3.1 PXRD Analysis
17
18
19 The crystallographic and phase purity verifications of the prepared sample were
20
21 determined from PXRD patterns. Fig. 1 shows the PXRD patterns of the Li2SiO3:xMn4+
22
23
24 phosphor synthesized in the current work. The XRD patterns clearly show that the undoped
25
26 Li2SiO3 crystal planes exhibit a similarity in both shape and position of diffracion peaks to
27
28
29
those of Li2SiO3 doped with 0.02 concentration of Mn. All of the peaks in PXRD patterns
30
31 were well indexed with the phase pure orthorhombic crystal structure of Li2SiO3, as per the
32
33 JCPDS file number 29-829[36]. It is notable that no peak corresponding to any second phase
34
35
36 was found. According to the valuable ionic radius (r) of Mn4+ ions should replace Li+ rather
37
38 than Si4+. This is said that there is a contraction of the host lattice cell after the smaller Mn 4+
39
40
41 replace Li+ in host lattice.
42
43
r1 (CN)−r2 (CN)
44 Dr = 100 ∗ (6)
45 r1 (CN)
46
47
48 Where, r1(CN) = the radius of the host cations, r2 = radius of doped ion, and Dr =
(CN)
49
50
51 radius percentage difference. If the radius difference between host cations and doped ion
52
53 exceeded than 30%, then new compound will produce. In our case, it is found Dr = 11% [6
54
55
56 (CN)] it should be Dr <15%. It indicates that the doping of Mn4+ ions have no influence on
57
58 the crystal structure of the Li2SiO3 system It is further confirmed that Li+ has been
59
60
61
62 5|Page
63
64
65
 successfully replaced by Mn4+ and incorporated into the Li2SiO3 hosts lattice [40]. The ionic
1
2 radius of host cationic and Mn4+ were listed in Table 1
3
4
5
6 Fig. 1 PXRD patterns of Li2SiO3:xMn4+ phosphors synthesized at 950oC
7
8
9 Table 1 Ionic radius between host cationic and Mn4+ in Li2SiO3:0.02Mn4+ phosphor
10
11
12
13
The cell parameters were obtained with the distance of a = 9.4107Ǻ, b = 5.4029Ǻ, c =
14
15 4.6605Ǻ and angle of α = β = γ = 90º. The Debye scherrer equation was used to calculate the
16
17 crystallite size from the diffraction peak [37].
18
19
20
0.941λ
21 D= (3)
βcosθ
22
23
24
25 Where D represent the mean crystallite size, for X-rays wavelength λ stands is used
26
27 (0.1540562 nm), diffraction angle is represent by θ, where as β represent the highest peak of
28
29
30 full width at half maximum (FWHM in radians). Using equation (3), it was determined that
31
32 the average crystallite or gain size was D = 38.26 nm.
33
34
35
36
Scherrer's formula only takes into account the impact of crystallite size on the XRD
37
38 peak broadening; however, it provides no information about the lattice's microstructures,
39
40 specifically the intrinsic strain that develops in nanocrystals as a result of point defects, grain
41
42
43 boundaries, triple junctions, and stacking faults[38]. In XRD data, the broadening (βT) of the
44
45 peaks is due to the combine effect of crystalline size (βD) and micro strain (βε) [39].
46
47
48
49 βT = βD + βε (4)
50
51
Kλ
52 βT = + 4εtanθ (5)
53 Dcosθ
54
55
1
56 δ = D2 (6)
57 s
58
59
60
61
62 6|Page
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64
65
 In which ε is the gradient (slope) of the line and Kλ/Dcosθ is y intercept. Accordingly,
1
2 the slope and y-intersect of the fitted line represent strain and particle size, respectively. The
3
4
5 plots showed a possive strain for the Li2SiO3. Here we calculated dislocation density (δ) using
6
7 equation (6), where Ds is the grain size that can be calculated using scherrer’s relation. It has
8
9
10 been observed that the dislocation density decrease with increse in crystallite size, which
11
12 indicates a lower number of lattice imperfection. The peak angles, Miller indices, FWHM,
13
14
15 crystallite size, dislocation density and microstrain of Li2SiO3:xMn4+ phosphors were
16
17 calculated and listed in Table 2
18
19
20
Fig. 2 Williamson- Hall plot of Li2SiO3:xMn4+ phosphor
21
22 Table 2 Peak angles, Miller indices, FWHM, crystallite size, dislocation density and
23
24 microstrain of Li2SiO3:xMn4+ phosphors
25
26
3.1 Rietveld Refinement Analysis
27
28
29
30 Fig. 3 shows the crystal structure of Li2SiO3:xMn4+ drawn with the program VESTA.
31
32 One kind of Li atoms, one type of Si atoms, and two types of O atoms make up its crystal
33
34
35 structure. Both Li and Si from the corner share a tetrahedral unit with nearby O atoms.
36
37 Li2SiO3:0.02Mn4+ Rietveld refinement findings are shown in Fig. 4, with black crosses and
38
39
40
red solid lines representing the observed and calculated patterns, respectively;The good
41
42 fitting parameters, Rp 4.60%, Rwp 7.40%, and chi square (χ2 ) 2.91, suggest the derived
43
44 samples are of high quality. The isotropic atomic displacement parameters of
45
46
47 Li2SiO3:0.02Mn4+ are provided in Table 3 along with the atomic coordinates, occupancies,
48
49 and pseudo-cubic perovskite structure that can be used to successfully index all of the peaks.
50
51
52
53 Fig. 3 Schematic view of the orthorhombic crystal structure of Li2SiO3 phosphor
54
55 Fig. 4 Riveted refinement plot of Li2SiO3:0.02Mn4+ phosphor
56
57
58 Table 3 Rietveld refinement crystallographic data of Li2SiO3:0.02Mn4+ phosphor
59
60 with CIF File of Li2SiO3
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62 7|Page
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64
65
 Table 4 Comparison of refinement crystallographic data for atomic parameters of
1
2 Li2SiO3:0.02Mn4+phosphorwith standard Li2SiO3
3
4
5
3.2 Thermal Analysis Thechnique
6
7
8 3.3.1 Differential scanning calorimetry (DSC)
9
10 DSC analysis was carried out to examine the thermal characteristics of the compounds
11
12
13
as they were produced. The DSC examined the thermal stability of the powders[41]. The
14
15 typical DSC curves of Li2SiO3:0.02Mn4+ are shown in Fig. 5(a) The sharp exothermic DSC
16
17 peak at about 81.47°C, which indicate chemical reaction occurring within the sample, with
18
19
20 heat being released. The area under the peaks in the graph represent the enthalpy change
21
22 associated with the corresponding thermal event. The heat of melting ∆Hm was determined
23
24
25 using the following relation.
26
27
28 Area under the melting peak
Heat of melting = (7)
29 heating rate
30
31
32 Evaluating the equation (7), heat of melting was calculated as -155.23 J/g.
33
34
35
36 3.3.2 Thermogravimetric (TGA)
37
38
39 Under various gas environment conditions, the sample mass changes as a function of
40
41 temperature or time using the (TGA) technique[42]. The TGA analyses of the
42
43
44 Li2SiO3:0.02Mn4+ complexes showing Fig. 5(b) that show the single stage assigned to the
45
46 loss of water molecule in the temperature interval from 550 to 650◦C and correspond to the
47
48
49 weight loss of 0.2 CO2 molecule. On the basis of the result from the TGA analysis, the cerate
50
51 particles prepared were calcined at 1000 ºC.
52
53
54 Fig. 5 (a) DSC and (b) TGA curve of Li2SiO3:0.02Mn4+ phosphor
55
56
57 3.3 Scanning Electron microscope (SEM)
58
59
60
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62 8|Page
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65
 In order to determine the surface morphology and particle size of these powders, SEM
1
2 was performed, and the SEM micrographs are represented in Fig. 6 (a, b, c) As observed that.
3
4
5 the particles show spherical morphology, micro-nano crystallite and there is also powder with
6
7 irregular shape because small particles with size below 2µm. and relatively narrow size
8
9
10 distribution of mean about 5 µm. Image J software was use to identify the mean particle size
11
12 by the histogram, as shown in Fig. 6(d).
13
14
15
16
Fig. 6 (a, b, c) SEM image with different magnification (d) Represent the particle size
17 distribution of Li2SiO3:0.02Mn4+ phosphor
18
19
20 3.4 Energy Dispersive X-ray (EDX)
21
22
23 The elemental composition of a phosphor sample can be identified and measured
24
25
26 using EDX, which is a standard method. EDX measurements were performed to confirm the
27
28 presence of Mn4+ in the synthesized Li2SiO3:0.02Mn4+ phosphor and to determine their
29
30
31 chemical compositions. Fig. 7(a) shows the EDX mapping of the Mn4+ doped Li2SiO3
32
33 samples. That EDX characterization demonstrated that four components lithium (Li), silicon
34
35
36
(Si), oxygen (O) and Manganese (Mn) were existed in the spherical particles but the EDX of
37
38 the matrix could not show the presence of lithium because of its lighter weight in Fig. 7(b)
39
40 [37].
41
42
43
44 Fig. 7 (a) EDX mapping (b) EDX spectra of Li2SiO3:0.02Mn4+ phosphor
45
46
47 Table 5 Chemical composition of Li2SiO3:0.02Mn4+phosphor
48
49
50
51 3.5 Fourier Transform Infrared Spectroscopy (FTIR)
52
53
54
55
The vibration properties of synthesized phosphor were studies by FTIR. Fig. 8 show
56
57 the FTIR spectra recorded for a Mn 0.02mol doped Li2SiO3 phosphor within the wavelength
58
59 range of 4000-400 cm-1 as a function of percentage transmittance. The peaks at 487.96 cm-1
60
61
62 9|Page
63
64
65
 are assigned to Si-O-Si bending vibration, the peaks at 610.79 731.84, 934.94 cm-1 are
1
2 assigned to O-Si-O symmetry stretching vibration, this indicates that SiO2 groups have
3
4
5 formed in the samples and at 1479.45cm-1 are assigned C=O stretching vibration, and
6
7 3564.75 cm-1 are assigned due to O-H stretching vibration. Also, the double peaks at around
8
9
10 2361 cm-1 is assigned to KBr [43]. All the peaks of prepared Li2SiO3:0.02Mn4+phosphor were
11
12 assigned and listed in Table 6.
13
14
15
16
Fig. 8 FTIR spectra of Li2SiO3:0.02Mn4+phosphor
17
18 Table 6 FTIR assignment of Li2SiO3:0.02Mn4+phosphor
19
20 3.6 Raman spectroscopy
21
22
23 The raman spectra of Li2SiO3:0.02Mn4+ phosphor recorded in the frequency range
24
25 100 to 1400 cm-1 are represent in Fig. 9. To within experimental errors, the wavenumbers
26
27
28 included in Fig. 9 agree with the data reported previously for Li2SiO3 by devarajan and
29
30 shurvell who actually reported 29 raman band[44]. The spectrum of Li2SiO3:xMn4+ contain
31
32
33 three major vibration mode situated at 507, 619, and 988 cm-1 which are fringerprint of
34
35 orthoromhbic structure. Which is assingned to Li-O stretching, Si-O-Si bending, and Si-O
36
37
38 bending respectively and lited in Table 7. The prominent vibration modes with frequencies
39
40 the range 450-760 cm-1 are common frequencies for most Mn-Oxides: they have been
41
42
43
interpreted by various researcher as Mn-O strech and bending modes arising from Mn4+O6
44
45 octahedra[45].
46
47
48 Fig. 9 Raman spectra of Li2SiO3:0.02Mn4+phosphors
49
50
51 Table 7 Raman vibrational modes of Li2SiO3:0.02Mn4+phosphors
52
53
54 3.7 UV-Vis Spectroscopic Studies
55
56
57 UV-Visible spectra of Li2SiO3:0.02Mn4+ phosphor in the wavelength range from 200-
58
59
60 500nm are shown in Fig. 10(a). Using optical absorption spectra, Tauc provided a method for
61
62 10 | P a g e
63
64
65
 calculating the band gap energy of amorphous semiconductors in 1966. His proposal was
1
2 further developed by Davis and Mott[46]. The Tauc approach is based on the notion that the
3
4
5 following equation can adequately represent the energy-dependent absorption coefficient[47].
6
7
8 (𝛼ℎ𝜈)1/𝑛 = 𝐴(ℎ𝜈 − 𝐸𝑔 ) (8)
9
10
11
12
where n can have values of 3, 2, 3/2, or 1/2, which, respectively, represent transitions
13
14 that are direct (forbidden), direct (allowed), indirect (allowed), and indirect (forbidden). As
15
16 show in Fig. 10(b) the direct allowed transition might be determined from Tauc's plot of
17
18
19 (αhν)2 vs hv. The band gap, Eg = 5.6 eV, is determined by the hv value at the point where the
20
21 horizontal axis and tangent line cross. which is large enough for the incorporation of the Mn4+
22
23
24 level.
25
26
27 Fig. 10 (a) Absorbance versus wavelength graph (b) Tauc plot of (αhν)2 versus (hν) for
28
band gap energy of Li2SiO3:0.02Mn4+ phosphor
29
30
31 3.8 Analysis of Photoluminescence Spectra
32
33
34 Fig. 11(a) and 12(a) shows the PLE spectra of Li2SiO3:0.02Mn4+ (for λex=425,
35
36
37
475nm) phosphors, respectively. Both the phosphors show broad excitation band covering
38
39 from 400 to 500 nm. The illuminating mechanism is typically explained using the Tanabe-
40
41 Sugano energy level diagram of the Mn4+ ion. The electrons in Mn4+ ion absorb the light
42
43
44 energy and are raised to the excited states (4T1, 2T2, and 4T2) from the ground state (4A2). The
45
46 electrons in higher excited states seek to return to the lower excited states, locate at the
47
48
49 excited state (2E) by nonradiative, and finally transfer to the ground state (4A2) by the 2E →
50
4
51 A2 transition, releasing photons and showing emission[16]. The red emission both originated
52
53
54
in the 2E → 4A2 radiative transition of Mn4+ in octahedral enviroment cause some vibrational
55
56 level near the 2E level and they participate in luminescence process[48]. In fig. () Tanabe-
57
58 Sugano energy level diagram to demonstrate the Li2SiO3:Mn4+ luminescence principle. field
59
60
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62 11 | P a g e
63
64
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 strength increases, the Mn4+ ion's 4f ground state energy level splits into 4A2, 4T2 and 2G into
1
2 2
E when Mn4+ absorb energy, electron transition from ground state 4A2 to the excited state 4T2
3
4
5 forming allowed transition. The non-radiation transition causes the excited electrons to
6
7 dissipate back to the lowest excited level 2E, while the radiation transition causes the excited
8
9
10 electrons at the final 2E level to emit red light (2Eg→4A2g). The following formula can be
11
12 used to estimate the local crystal feld strength from the energy gap of the 4A2g→4T2g
13
14
15 transition[49]
16
17
18 E (4A 2g → 4T1g )
19 Dq = (9)
20 10
21
22
23 The energy difference between 4A2 → 4T2and 4A2→4T1 can be used to calculate the
24
25
26 Racah parameter B using the following formula[36,49].
27
28
29 Dq 15(x − 8)
= 2 (10)
30 B (x − 10x)
31
32
33
34 The value of the Racah parameter C can be determined using the peak difference of 2E
35
36 → 4A2 from the PL spectra[49].
37
38
39
E (4A 2g →4T 1g )−(4A 2g →4T 2g )
40 x= (11)
41 Dq
42
43
44
45
E (2E g → 4T 2g ) 3.05C 1.8B
= − + 7.9 (12)
46 B B Dq
47
48
49
50 The values of Dq, B, and C for Mn4+ ions are calculated as 2353 cm- 1,-1743 cm- 1, and
51
52 8759.03 cm- 1
(for λex=425nm), 2105.26 cm-1, -1559.45 cm-1and 7953.84 cm-1 (for
53
54
55 λex=475nm) respectively. The computed value of Dq/B is approximately -1.3 and -1.35,
56
57 which is smaller than 2.1, representing that Mn4+ ions possess a week crystal field in the
58
59
60
Li2SiO3 host.
61
62 12 | P a g e
63
64
65
 Table 8 Represent the crystal field parameter, Racah parameter B, Racah parameter C
1 and Dq/B
2
3
4 The effect of Mn4+ doping concentration on the emission intensity of Li2SiO3 phosphor
5
6 was investigated. All the PL spectra exhibit the emission band centered at 642 nm (λex=425),
7
8
9
and 717 nm (λex=475), due to the spin-forbidden 2Eg→4A2g transition. It can be seen that the
10
11 position and shape of PL spectra has not change with the intensity of Mn4+ concentration for
12
13 both 425 nm and 475 nm exitation. Fig.11(b) and 12(b) shows how the emission intensity
14
15
16 increases as the Mn4+ concentration rises and reaches a maximum at 0.02mol; above this
17
18 point, concentration quenching is seen. A high dopant concentration reduces the distance
19
20
21 between the Mn4+-Mn4+ pairs in the host lattice, accompanied by means of a strong
22
23 interaction from one Mn4+ ion to any other[48]
24
25
26 Fig. 11 (a) Excitation (b) Emission spectra of Li2SiO3:xMn4+ (λex=425nm, λex=642nm)
27 phosphor
28
29 Fig.12 (a) Excitation (b) Emission spectra of Li2SiO3:xMn4+ (λex=475nm, λex=717nm)
30
31 phosphor
32
33 Fig.13(a) Schematic energy level diagram showing possible transitions of Li2SiO3:Mn4+
34
35 phosphor (b) Tanabe–Sugano energy level diagram for Mn4+ in the octahedral site of
36
37
38 Li2SiO3 host.
39
40
41 In order to clarify which mechanism is responsible for the concentration quenching, an
42
43
44 approximate estimation of the critical distance (Rc) is calculated according to the following
45
46 relationship[50]
47
48
49 1⁄
3V 3
50 R 𝑐 = 2 (4πx Z) (13)
51 c
52
53
54 where V stands for the volume of the unit cell, xc is the critical concentration of the
55
56
57 activator ion, and Z represents the number of sites in which the Mn4+ ion can substitute in a
58
59 unit cell. For Li2SiO3:0.02Mn4+, Z = 4, Xc = 0.02, and V = 237.676 Å3 . The Rc value is
60
61
62 13 | P a g e
63
64
65
 calculated to be 17.8 Å, t is well known that, when the Rc < 5 Å exchange interactions are
1
2 usually predominant. In our case, Rc > 5 is non-radiative energy transfer was mostly
3
4
5 attributable to electric multipolar interactions in Li2SiO3:xMn4+ phosphors. The energy
6
7 migration mechanism between Mn4+ in Li2SiO3 is impossible to attribute the exchange
8
9
10 interaction except electric multipolar interaction. This may be established using Dexter's
11
12 theory as follows[51].
13
14
15 I θ⁄ −1
16 = K[1 + β(x) 3] (14)
x
17
18
19
20
I stands for emission intensity, x for activator ion concentration no less than the
21
22 critical concentration, K and β are for constant under the same host and excitation conditions,
23
24 and equals 6, 8, and 10 for the dipole-dipole (d-d), quadrupole-quadrupole (q-q), dipole-
25
26
27 quadrupole (d-q), and respective interactions. The value of the θ is obtain from the linear
28
29 fitting plot of ln(I/x) vs ln(x) (Fig.15), the slope of the fitting line (-θ/3) is -1.2508 and -
30
31
32 1.3734. The value of θ is close to 6, indicating that electric d-d interactions are the
33
34 predominant concentration quenching mechanism among Mn4+ in the Li2SiO3.
35
36
37 Fig. 14 Emission intensity of Li2SiO3 on dependence of Mn4+ mol concentration
38
39
40 Fig. 15 Linear fitting graph of Li2SiO3:xMn4+ phosphors
41
42 3.9 Lifetime measurment
43
44
45
46 Fig. 16 depicts the results of the luminescence lifetime measurements of the
47
48 Li2SiO3:0.02Mn4+ phosphors under the excitations at 425 and 475 nm with emission
49
50
51
wavelengths of 642 and 717 nm corresponding to 2Eg→4A2g transitions, respectively The
52
53 decay curves can be well fitted by double exponential decay function describe by the
54
55 following equation (15)[37].
56
57
58 −x⁄ −x⁄
59 y = y0 + A1 ∗ exp t1 + A1 ∗ exp t2 (15)
60
61
62 14 | P a g e
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64
65
 Here y and y0 are luminescence intensity at time t and 0, A1 and A2 are constant and
1
2 fast decay, and slow decay is described by t1 and t2 in the Mn4+ doped Li2SiO3 sample. The
3
4
5 average decay time (ꞇ) can be determined using the equation (16) which is given below[52]
6
7 A1 τ1 2 +A2 τ2 2
8 τ= A1 τ1 +A2 τ2
9
10
11 (16)
12
13 The average life time of the sample Li2SiO3:0.02Mn4+ were calculaed as 4.9ms (for
14
15
16 λex=425nm) and 0.4ms (for λex=475nm), respectively.
17
18 Fig. 16 Decay curve of Li2SiO3:0.02Mn4+ phosphor
19
20
21
Table 9 Fitting result of the Li2SiO3:0.04Tb3+ phosphor
22
23
24 3.10 Commission Internationale de l'Elcairage(CIE)
25
26
27 The CIE color coordinate system is a standard method used to represent colors in a
28
29
30
numerical way. The internationl Commission on lllumination (CIE) developed this system,
31
32 and it is widely used in color science and industries. Therefore, the CIE chromaticity diagram
33
34 of Li2SiO3:xMn4+ was drawn by CIE software. CIE chromaticity diagram were determined
35
36
37 for 0.01 to 0.05 mol Mn4+ doped Li2SiO3 samples. The prepared phosphors' determined CIE
38
39 colour chromaticity coordinates (x, y) are situated in the red area of the CIE chromaticity
40
41
42 map, as illustrated in Fig. 17.
43
44
45 Fig. 17 The typical CIE 1931 chromaticity diagram of Li2SiO3:xMn4+ phosphor
46
47 3.11 Color Purity
48
49
50
51 Based on equation(17), the color purity of all samples was calculated[53]
52
53
54 √(x−xi )2 +(y−yi )2
color purity = × 100% (17)
55 √(xd −xi )2 +(yd −yi )2
56
57
58
59
60
61
62 15 | P a g e
63
64
65
 These coordinates correspond with the CIE coordinates of the sample point (x,y),
1
2 standard source (xi, yi), and dominant wavelength (xd, yd) respectively. (xi, yi) had a value of
3
4
5 (0.33, 0.33). As shown in Table 10 the color purity of the Li2SiO3:xMn4+ very high for the
6
7 synthesized sample. Therefore, the color purity of red light is evaluated to be 100%.
8
9
10
11 3.12 Color Rendering Index (CRI)
12
13
14 The ability of a light source to emit colour is also indicated by the CRI, which is
15
16 another crucial criterion to assess a light source's lighting quality. The CRI value is a
17
18
19 numerical value that ranges from 0 to 100[54]. Where a higher value indicates better color
20
21 rendering. we have calculated the CRI value by equation (18).
22
23
24 1
25 CRI = 8 ∑8i R i (18)
26
27
28 A.Verma et al. have already described the method for calculating the CRI[55].
29
30
31 Calculated CRI values in this work range from 12 to 17, indicating the prepared
32
33 Li2SiO3:xMn4+ phosphor exhibits low CRI range for red color.
34
35
36 3.13 Quantum Efficiency (QE)
37
38
39 Quantum efficiency (QE) is an important parameter to evaluate the properties and
40
41 application potentials of phosphor. QE is another crucial factor that limits the phosphors
42
43
44 application and the parameter can be obtained using the following equation (19)[55].
45
46
47 ISam.
48 Q. E = (19)
Eref. − ESam.
49
50
51
52 Where, Isam. = PL intensity of emission spectra of the samples, Esam= PL intensity of
53
54 excitation spectra of samples, Eref = PL intensity of excitation spectra of reference. The QE
55
56
57 value of the discussed materials were increases as the Mn4+ doping concentration increases
58
59 from 0.01, 0.02 mol and then slightly reduces.
60
61
62 16 | P a g e
63
64
65
 Table 10 Photometric parameters of Li2SiO3:xMn4+phosphors
1
2 4. Conclusion
3
4
5
6 A red Li2SiO3:xMn4+ phosphors were synthesized by solid‐ state reaction technique.
7
8 The compound crystallizes in the orthorhombic structure and Cmc21 space group, according
9
10
11 to the XRD refinement. Raman spectra exhibit the characteristic vibrational band associated
12
13 with the host lattice and dopant ion. The band gap based on Tauc’s plot calculation is direct
14
15
16
allowed transition with the value of ~5.6 eV and consists with the experimental value.
17
18 Luminescence properties of the Li2SiO3:0.02Mn4+ phosphor was analyzed by measuring the
19
20 excitation spectra, emission spectra and lifetime. The broad excitation band in the range of
21
22
23 400-500 nm with strongest peak at around 425 nm, 475 nm and can give red luminescence
24
25 centered at 642 and 717 nm, respectively. The Mn4+ optimal doping concentration is 0.02, at
26
27
28 which concentration quenching of both phosphors occurs due to energy transfer between
29
30 neighboring Mn4+ ions based on d-d interaction. The phosphors can both give strong red
31
32
33
emission, the phosphor showed excellent CIE chromaticity co-ordinates (x, y) in red region
34
35 and 100% color purity both the excitation spectra under visible region, respectively. All the
36
37 results indicate that the Li2SiO3:xMn4+ phosphor has potential in the WLED application.
38
39
40
41 Funding
42
43 The corresponding author Ishwar Prasad Sahu, is thankful to University Grant Commission
44
45
46 (UGC) for the UGC-BSR Start-up Fellowship (No. F.30-420/2018 (BSR), dated 23/10/2018),
47
48 Government of India.
49
50
51 Conflict of Interest
52
53
54 On behalf of all authors, the corresponding author states that there is no conflict of interest.
55
56
57
58 Research Data Policy and Data Availability Statements
59
60
61
62 17 | P a g e
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64
65
 The author’s states that analysed and relevant data of synthesized materials, which are
1
2 including and described in the manuscript will be freely available to researchers and scientists
3
4
5 who are working purpose of research and social welfare.
6
7 Author statement
8
9
10 Priya Barik and Ishwar Prasad Sahu: Investigate, designed the whole research,
11
12 Conceptualization, synthesized all the samples, and collected experimental data, Data
13
14
15 plotting, writing of the manuscript, review, editing and formatting, and editing of manuscript
16
17 corresponding to the journals. Aksh Kumar Verma manuscript editing, thoroughly analysis
18
19
and revised the articles review. Anjali Mehto proposed many good suggestions.
20
21
22
23 Declaration of competing interest
24
25
26 The authors declare that they have no known competing financial interests or personal
27
28 relationships that could have appeared to influence the work reported in this paper.
29
30
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Table Click here to access/download;Table;Mn table.docx

List of Table:

Table 1 Dr between host cationic and Mn4+ in Li2SiO3:0.02Mn4+ phosphor

S.N. Mn4+ Ionic radius (r2) in Ǻ Li+ Ionic radius (r1) in Ǻ Si4+ Ionic radius in Ǻ
1 CN = 6 CN = 8 CN = 6 CN = 4 CN = 6 CN = 4
2 0.67 0.92 0.76 0.59 0.40 0.26

Table 2 Peak angles, Miller indices, FWHM, crystallite size, dislocation density and micro strain of Li2SiO3:xMn4+ phosphors

Sample 2θ Miller β Ds δ DW-H Micro

(Degree) indices strain
ε
Li2SiO3 27.13644 0.16506 49.49222 0.0004082 55.000 0.00118

Li2SiO3:0.01Mn4+ 27.04276 0.18824 43.38917 0.0005311 50.036 0.00120

Li2SiO3:0.02Mn4+ 27.11435 [1 1 1] 0.15189 53.78107 0.0003457 69.300 0.00212

Li2SiO3:0.03Mn4+ 27.08145 0.18588 43.94363 0.0005178 60.789 0.00173

Li2SiO3:0.04Mn4+ 27.09176 0.15900 51.37374 0.0003788 73.333 0.00181

Li2SiO3:0.05Mn4+ 27.95197 0.14465 56.45368 0.0003137 68.275 0.00147

Table 3 Rietveld refinement Crystallographic data Li2SiO3:Mn4+ phosphor with CIF File of Li2SiO3

S.N. Refinement parameters Refinement Values of Li2SiO3 As per CIF File:

Li2SiO3:0.02Mn4+phosphor 2310662
1 Empirical Formula Li2SiO3:0.02Mn4+ Li2SiO3
2 Formula weight 90.5193 89.9657
3 Crystal System Orthorhombic Orthorhombic
4 Space group Cmc21 Cmc21
5 Space group number 36 36
6 Laue Class: mmm -----------
7 Unit Cell Parameters a = 9.40755 Å, b = 5.40968 Å,c a = 9.36000 Å, b = 5.39500 Å,
= 4.67022 Å, α = β =γ = 90° c = 4.67500 Å, α= β =γ = 90°
8 Vol: 237.676 Å3 236.074410 Å3
9 Calculated density 2.412 g/cm3 -----------
10 Z 4 4
11 Rp : 4.60 -----------
12 Rwp: 7.40 -----------
13 Rexp: 4.04 -----------
14 Chi(χ2): 2.91 -----------
15 RBragg -factor: 6.1 -----------
16 RF-factor 4.19 -----------
17 DW-Stat.: 0.2494 -----------
18 GoF Index 3.1 -----------
19 DW-exp 1.8767 -----------
Table 4 Comparison of refinement crystallographic data for atomic parameters of Li2SiO3:0.02Mn4+phosphor with standard
Li2SiO3

Atom Atomic Co-ordinate Biso Occupancy/sof Mult.

x y z
Std. doped Std. doped Std. doped Std. doped Std. doped

O1 0.14100 0.15272 0.32100 0.35571 0.450 0.69036 1.000 -2.276 1.000 2.626 8

O2 0.00000 0.00000 0.10000 0.08615 0.860 1.12611 1.000 -2.327 1.000 0.941 4

Li1 0.16000 0.13168 0.32000 0.24817 0.000 0.00000 1.000 22.157 1.000 4.162 8

Si1 0.00000 0.00000 0.16400 0.14198 0.537 0.76217 1.000 2.786 1.000 0.974 4

Table 5 Chemical composition of Li2SiO3:0.02Mn4+ phosphor

S.N. Element Line Atomic% Weight %

1 O K 74.56 62.06
2 Si K 24.89 36.37
3 Mn K 0.55 1.57
Total 100 100
 Table 6 FTIR assignment of Li2SiO3:0.02Mn4+phosphors

Sample Name Frequency(Cm-1) Assignment Type

487.96 cm-1 O-Si-O Bending Vibration
610.79,731.84,846.78, 934.94 cm-1 Si-O-Si Symmetry Stretching
Li2SiO3:0.02Mn4+
1479.45 cm-1 C=O Stretching Vibration
3570.33 cm-1 O-H Stretching Vibration

Table 7 Raman vibrational modes of Li2SiO3:0.02Mn4+phosphors

Mode Wavenumber (cm-1) Assignment

υ1 215, 238 cm-1 Li-O stretching

υ7 338, 370, 379 cm-1 Li-O stretching, O-Si-O bending

υ8 423 cm-1 O-Si-O bending

υ9 448 cm-1 Li-O stretching, O-Si-O bending

υ10 507, 575 cm-1 Li-O stretching

υ13 619 cm-1 Si-O-Si bending, Si-O

υ17 988 cm-1 Si-O bending

υ18 1042, 1100 cm-1 Si-O stretching, O-Si-O bending

 Table 8 Represent the crystal field parameter, Racah parameter B, Racah parameter C and Dq/B

Sample Name Dq B C Dq/B

Li2SiO3:0.02Mn4+(λex=425nm) 2353.00 -1743.00 8759.03 -1.3

Li2SiO3:0.02Mn4+(λex=475nm) 2105.26 -1559.45 7953.84 -1.35

Table 9 Fitting results of the Li2SiO3:0.02Mn4+phosphor

Sample Name R2-Value τ1 (ms) τ2 (ms) A1 A2 τ average (ms)

Li2SiO3:0.02Mn4+(λex=425nm) 1 280.8607 2723.2338 5342.83919 44154.04016 4.99

Li2SiO3:0.02Mn4+(λex=475nm) 1 322.1546 731.29480 123726.920 38054.97500 0.49

 Table 10 Photometric parameters of Li2SiO3:xMn4+phosphors

Sample Name CIE color co-ordinate Dominant CIE Color CRI CP QE

(X, Y) Co-Ordinate (Xd, Yd) (%) (%)

λex=425 nm λex=475 nm λex=425 nm λex=475 nm λex=425nm λex=475nm

Li2SiO3:0.01Mn4+ (0.6858, 0.3141) (0.6886, 0.3112) (0.6858, 0.3141) (0.6858, 0.3139) 13 17 100 68

Li2SiO3:0.02Mn4+ (0.6843, 0.3155) (0.6881, 0.3117) (0.6881, 0.3117) (0.6844, 0.3153) 13 17 100 70.51

Li2SiO3:0.03Mn4+ (0.6834, 0.3164) (0.6881, 0.3120) (0.6879, 0.3119) (0.6835, 0.3162) 12 17 100 64.15

Li2SiO3:0.04Mn4+ (0.6838, 0.3160) (0.6866, 0.3133) (0.6865, 0.3132) (0.6837, 03160) 12 17 100 61

Li2SiO3:0.05Mn4+ (0.6833, 0.3165) (0.6860, 0.3139) (0.6858, 0.3139) (0.6832, 0.3165) 12 16 100 57.77
Graph Click here to access/download;Figure;Mn all graph2.docx

List of Figures:

Li2SiO3 : 0.05Mn4+

Li2SiO3 : 0.04Mn4+

Li2SiO3 : 0.03Mn4+
Intensity (a.u.)

Li2SiO3 : 0.02Mn4+

Li2SiO3 : 0.01Mn4+

Li2SiO3- Host

JCPDS file no. 29-829

[131]
[130]
[ 1 1 1]
[020]

[060]
[202]
[221]

[311]

[402]

[414]

[418]
[328]
[ 1 3 8]
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

2q (Degree)
Fig. 1 X-ray diffraction patterns of Li2SiO3:xMn4+ different concentration synthesized at 950oC
 Li2SiO3:0.05Mn4+
 Linear Fitted curve

Li2SiO3:0.04Mn4+
 Linear Fitted curve

Li2SiO3:0.03Mn4+
 Linear Fitted curve
bCosq

Li2SiO3:0.02Mn4+
 Linear Fitted curve

Li2SiO3:0.01Mn4+
 Linear Fitted curve

Li2SiO3: Host
 Linear Fitted curve

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
4Sinq
Fig. 2 Williamson- Hall plot of Li2SiO3:xMn4+ phosphor
Fig. 3 Schematic view of the orthorhombic crystal structure of Li2SiO3 phosphor
 Li2SiO3: 0.02 Mn4+

Fig. 4 Riveted refinement plot of Li2SiO3:0.02Mn4+ phosphor

 9.8
0 Li2SiO3:0.02Mn4+ Li2SiO3:0.02Mn4+

-1
9.7
Heat flow (mW)

weight loss (%)

-2

9.6
-3 0.2 %
Area = -155.23 mJ
Peak = 81.47
-4
Onset = 40.25 °C
9.5
Endset = 132.75 °C
-5

-6 9.4
Melting and fusion

0 100 200 300 400 500 100 200 300 400 500 600 700 800 900 1000
Temperature (°C)
Temperature (C)

Fig. 5 (a) DSC and (b) TGA curve of Li2SiO3:0.02Mn4+ phosphor

 (a)
(c) (b)

(c) (d) Li2SiO3:Mn4+

5
Mean = 1.77 mm

Count
3

0
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8
Particle size (mm)

Fig. 6 (a, b, c) SEM image with different magnification (d) Represent the particle size distribution of Li2SiO3:Mn4+ phosphor
(a) (b)

Fig. 7 (a) EDX mapping (b) EDX spectra of Li2SiO3:0.02Mn4+ phosphor

 120

Li2SiO3:0.02Mn4+
100

Transmittance (%)
80

1479.45 cm-1
2361 cm-1
60

1049.13 cm-1

610.79 cm-1
40

731.84 cm-1
934.94 cm-1
846.78 cm-1
20

-1
487.96 cm
0

-20
4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wavenumber (cm )

Fig. 8 FTIR spectra of Li2SiO3:0.02Mn4+phosphor

 9000
Li2SiO3:0.02Mn4+
8000

619
Raman Intensity (a. u.) 7000

507
6000

379
5000

988
448
4000

1042
423

1100
575
3000 370
338
215
238

2000

1000

0
200 400 600 800 1000 1200 1400

Wavenumber (cm-1)

Fig. 9 Raman spectra of Li2SiO3:0.02Mn4+phosphor

 Li2SiO3:0.02Mn4+
4.0
Tauc Plot of Li2SiO3:0.02Mn4+
600

3.5
500

(ahv)2 (ev cm-1)2

Absorbance (a.u.)
3.0 400

300
2.5
200

2.0
100

1.5 0
Eg = 5.6 eV

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

1.0 Energy (eV)

0.5
200 250 300 350 400 450 500
Wavelength (nm)

Fig. 10 (a) Absorbance versus wavelength graph (b) Tauc plot of (αhν)2 versus (hν) for band gap energy of Li2SiO3:0.02Mn4+ phosphor
 Li2SiO3: 0.01 Mn4+ 1000
(a) (b) Li2SiO3: 0.02 Mn4+
Li2SiO3: 0.03 Mn4+
Li2SiO3: 0.04 Mn4+ 800

475 nm

Intensity (a.u.)
Li2SiO3: 0.05 Mn4+

717 nm
600

400

200

n
io
0.01

r at
nt
ce
on
0.02

c
nt
re
ffe
0.03

di
th
wi
n4+
0.04

3:M
O
2Si
0.05

Li
400 450 500 550 600 650 700 750
Wavelength (nm)

Fig.11 (a) Excitation (b) Emission spectra of Li2SiO3:xMn4+ (λex=475nm, λex=717nm) phosphor
 Li2SiO3: 0.01 Mn4+ 700
(a) (b) Li2SiO3: 0.02 Mn 4+

Li2SiO3: 0.03 Mn4+ 560

425 nm

642 nm
Li2SiO3: 0.04 Mn4+

Intensity (a.u.)
Li2SiO3: 0.05 Mn4+
420

280

140

0.01

n
io
at
r
nt
0.02

ce
on
c
nt
re
0.03

ffe
di
th
wi
0.04

n4+
3:M
O
2Si
0.05

Li
350 400 450 500 550 600 650 700 750

Wavelength (nm)

Fig. 12 (a) Excitation (b) Emission spectra of Li2SiO3:xMn4+ (λex=425nm, λex=642nm) phosphor
 (a) (b)

Fig.13 (a) Schematic energy level diagram showing possible transitions of Li2SiO3:Mn4+ phosphor (b) Tanabe–Sugano energy level
diagram for Mn4+ in the octahedral site of Li2SiO3 host.
 717nm
1000 642nm

Intensity (a. u.) 800

600

400

200

0
0.01 0.02 0.03 0.04 0.05
Mn4+ Mol concentration

Fig. 14 Emission intensity of Li2SiO3 on dependence of Mn4+ mol concentration

 5.0
Li2SiO3:Mn4+(lex=425nm)
Li2SiO3:Mn4+(lex=475nm)
4.8 Linear Fit of Li2SiO3:Mn4+(lex=425nm)
Linear Fit of Li2SiO3:Mn4+(lex=475nm)

4.6
Log (I/X)
4.4

4.2

Equation y = a + b*x
4.0 Plot B C
Weight No Weighting
Intercept 1.9368 ± 0.32454 2.58597 ± 0.09255
Slope -1.37348 ± 0.20245 -1.25084 ± 0.06223
3.8 Residual Sum of Squares 0.03744 6.82522E-4
Pearson's r -0.96892 -0.99753
R-Square (COD) 0.93881 0.99507
Adj. R-Square 0.91841 0.99261
3.6

-2.0 -1.8 -1.6 -1.4 -1.2

Log(X)

Fig. 15 Linear fitting graph of Li2SiO3:xMn4+ phosphors

 Li2SiO3:Mn4+(l=425 nm) Li2SiO3:Mn4+(lex=475 nm)
160000
50000 Exp.Dec fitted curve Exp.Dec fitted curve
Model ExpDec2
140000 Model ExpDec2
y = A1*exp(-x/t1) + A2*exp(-x/t2) +
Equation y = A1*exp(-x/t1) + A2*exp(-x
40000 y0
Equation
Intensity (a.u.)

120000 /t2) + y0

Intensity (a.u.)
Plot B
y0 50.86021 ± 16.67273 Plot B
30000 A1 5342.83919 ± 356.79116 100000 y0 118.87749 ± 3.64917
t1 280.86027 ± 29.35072 A1 123726.92772 ± 833.28828
A2 44154.04016 ± 144.35696 80000 t1 322.15467 ± 2.83903
t2 2723.23389 ± 10.0953
20000 A2 38054.97509 ± 933.6607
Reduced Chi-Sqr 447855.65093
60000 t2 731.2948 ± 5.25742
R-Square (COD) 0.99526
Adj. R-Square 0.99525 Reduced Chi-Sqr 605.61897
10000 40000 1
R-Square (COD)
Adj. R-Square 1
20000
0
0
0 2 4 6 8 10 12 14 16 18 20 0 1 2 3 4
Time (ms) Time (ms)

Fig.16 Decay curve of Li2SiO3:0.02Mn4+ phosphor

 Li2SiO3:0.02Mn4+ (λex=425nm)
Li2SiO3:0.02Mn4+ (λex=475nm)

Fig. 17 The typical CIE 1931 chromaticity diagram of Li2SiO3:xMn4+ phosphor