Solar Energy Materials 3 (1980) 519-532

~) North-Holland Publishing Company

LOW COST ELECTROLESS NICKEL BLACK COATINGS

FOR P H O T O T H E R M A L C O N V E R S I O N

S. N. KUMAR, L. K. MALHOTRA and K. L. CHOPRA

Thin Film Laboratory Dept. oJ Physics and Centre of Materials Science and Teeh.,
Indian Institute qf Technolofy, New Delhi 110 016, India

Received 27 March 1980: in revised form 12 May 1980

An economically viable electroless process, different from the conventionally used chemical
conversion methods, has been developed to deposit nickel black on galvanized iron. Coatings with
integrated absorptance (c~)lying between 0.90-0.93 and total emittance at 100 C =0.073 to 0.1 and
stable upto 200 C have been obtained. The coatings contain Ni and Zn particles embedded in a
suitable matrix of NiO, Ni20 3 and NiTP 3. The coatings contain practically no sulphides and hence
are less susceptible to humidity degradation processes.

1. Introduction

The role of spectrally selective surfaces for the efficient photothermal conversion
of solar energy is well established and excellent reviews on the subject are now
available [1-4]. Selective absorption has been accomplished by a number of tech-
niques and using a variety of materials. In addition to having a high integrated
absorptance (~) in the solar spectrum and a low emittance (e) in the infrared, the
coating materials and the fabrication techniques should be such as to lertd themselves
to large scale, high volume production and be economical both in production cost
and energy balance of fabrication. With these aims in view, we have developed a
process, electroless in nature, for the deposition of selective blacks on galvanized iron.
The present paper reports our results on "Electroless Nickel Black" the name we give
to our coating, since it is different from the usual black nickel coatings reported so far.
Our process, being a single step one, demands lower labour and equipment costs
and permits easy handling. The total coating cost comes to about ¢6/ft 2 as compared
with about ¢ 1 5 / f t 2 foI the electrodeposited black nickel coatings. Further since the
process is an electroless one, taking place at about 30°C, there is no need for power
supplies, electrical contacts, bus bars and electrical measuring instruments. The
process is different from the chemical conversion techniques in that in our process
the coating is obtained by a controlled chemical reduction that is catalyzed by zinc
whereas chemical conversion process generally involves an oxidizer or sulfidizer.
Although the bath itself does not contain any zinc salt, nevertheless, during deposi-
tion, zinc atoms from the substrate diffuse to the top surface (as seen by ESCA
chemical mapping) so that a catalyzed surface is available for further coating. More-
519
520 S. \ K u m a r el al. 1,21eclrol('.~s nickel H a c k coatin(t~

over, since our coatings contain practically no sulphides, whereas most chemical
conversion coatings do, the humidity degradation processes, wherein the sulphides
are converted into hydroxides and oxides with an accompanied degradation in
optical properties, are not likely to occur.

2. Experimental

Commercially available galvanized iron substrates (7 × 5 cm 2) were moistened,

rubbed with a detergent powder to remove stains and greases and then washed with
water. This was followed by dipping in an alkaline solution, washing with water,
then dipping in a dilute acid and subsequently washing with water. An active sub-
strate thus prepared was ready for deposition. The coating solution primarily con-
tained nickel, ammonium, sodium, sulphate, acetate and hydroxyl ions along with a
suitable reducing agent and organic additives (these organic additives take part
only in the chemical kinetics of the deposition process but do not get incorporated
into the coating)Z Deposition was carried out by alternate dip and exposure method.
Various coating parameters optimized for the deposition include bath composition
and temperature, pH and the dipping and exposure times. The pH was maintained
in the range 9.5-10.5. The process was scaled up to coat panels of size 54 × 16 cm 2
for outdoor studies with equally good and reproducible results. The coated samples
were washed with water and then air dried.
Different measurements of monochromatic reflectivity, i.e., specular reflectivity
and hemispherical reflectivity in the 0.35-13.5 # m range, and also the bidirectional
measurements of specular reflectivity around a given angle of incidence (10°) and
wavelength (2.12 izm) were performed at the Laboratoire d' Optique des Solides,
Paris. The details of their instrument have been reported by Behaghel et al. [5].
Integrated absorptance ~ and total emittance e were calculated from the room
temperature measurements of the hemispherical reflectivity. The ratio was also
obtained from a calorimetric method set up in our laboratory, similar to the one
described by Blickensderfer et al. [6]. The total emittance at different temperatures
was also obtained by comparing the signal from the specimen with that of a black
body, using an ellipsoidal aluminium concentrator and a Kipp & Zonen standard
thermopile.
The central line average roughness of the films was measured with a Taylor and
Hobson talystep instrument. The electron diffraction studies were made with an
AEI-EM 802 electron microscope and the surface micrographs obtained using a
Cambridge $4-10 type scanning electron microscope. A PHI 590A (SAM/ESCA)
instrument was used for Auger electron spectroscopic analysis, depth profiling and
for finding the chemical state of the elements constituting the coating.

3. Results and discussion

Visual inspection of the coatings under normal incidence revealed them to be black
and lustreless whereas they appeared in some parts to be shining and bluish-black
 ,S ., et al Electroless nickel black coatings 521

lOO

80
>-

>

w
_J

60

m
"0

I I
0.1 i/ ; ~ I'o 20 100
,k (MICRONS)

Fig. I. Specular reflectivity of electroless nickel black at an angle of incidence 0 = 10

1.0

0.5

0.0 I -- I I I ~ I.
e-2 ~ 6-1 ° o 0.1 ° 0.2

Fig. 2. Angular dispersion of normalized reflectivity around the specular angle for radiation incident at an
angle 0 = 10~ and wavelength 2 =2.15/~ m for (dashed curvel an Au specular mirror and (full curvel for a
selective sample.
!Ji
 S. N. Kumar et al. / Electroless nickel black coatin(4s 523

Fig. 3.(dl.

Fig. 3. (el.

Fig. 3. Surface profile scans obtained using a Talystep instrument of samples coated for various times :
(a) substrate, (b) 40 s, (c) 60 s, (dl 90 s, (e) 105 s.

when seen under grazing incidence. Fig. 1 gives the specular reflectance of a typical
sample. The fact that the coatings are comparatively smooth is clear from fig. 2
where the reflectivity of a specular gold mirror around the specular angle (0 = 10c,
2 = 2.12 ltm, p-polarization) and the normalized reflectivity of the sample relative to
the specular Au mirror have been plotted. The spreading of the curve for the gold
sample is not due to a scattering effect ; it merely reflects the characteristics of the
measuring system. The width at half height for the Au mirror gives the instrument
function S 1 = 1° 14' whereas the width at half height for the sample S 2 = 1° 26'. The
small difference indicates that the roughness of the coating is quite small. The smooth-
ness of the coatings is further confirmed by the surface profile scans obtained by the
_,4 3, X~. K u m a r el al. E / e c t r o l e s s nickel b l a c k ~mlin~ s'

talystep instrument. Roughness measurements were done for samples coated lk~r
various deposition times and the central line average roughness values then calcu-
lated. The surface profile scans are shown in fig. 3 and the average roughness values
calcuJated from them given in table 1. It can be seen that the roughness gradually
increases with plating time and reaches a maximum value of 1.804 just before thc
optimum plating time of 105 s. This is probably because a major portion of the
coating starts falling off at this stage and gives rise to maximum roughness. Further
increase in plating time gradually builds up the voids thus caused and, at the optimum
plating time (105 s), the surface is smoothly filled. The surface thus formed is smoother
than the initial galvanized iron substrate as is seen by its average roughness value. A
further increase in plating time gradually increases the coating thickness and slightly
increases the roughness. The optimum thickness of the coating was about 650 ~.
The surface topography of the unannealed coatings and the coatings annealed
(in airt at various temperatures for various times was examined using a SEM. Some
typical SEM photomicrographs are shown in figs. 4 7. In fig. 4 is shown the surface

~1able I
Falystep central lille a~,erage roughness values for various plating times

Sample hum ber Plating time ( s ~ Average roughness value

1 (} 0.996
2 40 0.816
3 60 O.767
4 9O 1.804
5 105 (I.723

Fig. 4. SE M photomicrograph of electroless nickel black c~)ating.

 S. N. Kumar et al. Electroless nickel black coatinqs 525

Fig. 5. SEM photomicrographs of selective samples annealed at 150' C in air for various times (al 5 h.
(bt 10 h, tc) 20 h.
526 5 \ Ixunl~lr c! u/ l:'h'ctt'oh'~v nickel h/at~, coultt~t~

Fig. 6. SEM p h o t o m i c r o g r a p h s of selective samples annealed at 200 (' in air l'or (aJ 5 h. Ib) 10 h. (cl 20 h.
 S. N. Kumar et al, / Electroless nickel black coatings 527

Fig. 7. SEM photomicrographs of selective samples annealed at 250cC in air for (a) 5 h, (b) 10 h, (c) 20 h.
528 .S. \~. K , m a r el ~t. Eleclrole.~s nickel h i , o k uo~ltin#s

topography of a typical unannealed coating. The SEM photomicrographs of the

samples annealed at 150°C for 5, 10 and 20 h are shown in fig. 5. As is evident, anneal-
ing for 5 h does not produce any significant change in the surface topography. Anneal-
ing for 10 h results in the formation of large grains. A photomicrograph of the sample
annealed for 20 h shows a further increase in grain size and the presence of voids
in the deposit. The surface topographies of samples annealed at 200°C for 5, 10 and
20 h are shown in fig. 6. The same general trend is observed here also except that the
grains now start growing into columns for 20 h heating. Finally, fig. 7 shows the SEM
photomicrographs of samples annealed at 250°C for 5, 10 and 20 h. In this case, the
formation of grains seems to start early with the result that the sample heated for 5 h
shows the formation of large grains. For 10 h heating, the grains seem to even out on
the entire surface. Heating the sample for 20 h causes a visible change in the colour
of the sample which changes to greyish black and this is probably reflected by the
unusual morphology of the deposit observed.
Fig. 8 shows the wavelength dependence of the total reflectivity of one of the
samples. The ~ and ~ values calculated from this curve are shown in table 2. For this
purpose, the data on solar irradiance given by Thekaekara [7] (for air mass one, a
very clear sky with the total amount of water and ozone of 20 mm and 3.4 mm
respectively and the wavelength exponent and the Angstrom coefficient, which

1O0 - -

80

60

z.O

20

o I I I I L I
0.1 I 3 5 10 20 I00
/~ ( microns )

Fig. 8. Total reflectivity of the sclective sample as a function of wavelength from 0.3 -13.5/~m.
 S. N. Kumar et al. / Electroless nickel black coatings 529

Table 2
Integrated absorptance ~ and the total emittance e
(calculated for 20, 100, 150 and 2 0 0 C from room
temperature measurements of the total reflectivity)

Temperature T Integrated
(C) Emittance absorptance

20 0.049 0.90
100 0.073 0.90
150 0.089 0.90
200 0.105 0.90

govern the atmospheric turbidity, of 0.66 and 0.085 respectively) has been used. A
significant feature of the reflectance curve is the lack of interference ripples in the
visible part of the curve. The ~ and e values calculated from the calorimetric and the
radiometric methods agree very well with those calculated from the total reflectivity
data. Coatings having e as large as 0.93 have been obtained but these coatings have
an ~ at 100°C approaching 0.1. The minimum value of e. at 100*C was 0.055 and this
coating gave an integrated absorptance of about 0.85. No significant change in
and e values has been observed in samples heated in air at 150 and 200°C for as long
as twenty hours but samples heated at 250°C for twenty hours showed a decrease in
of about 0.05.
The AES (Auger Electron Spectroscopy) analysis, performed by a SUPER SAM/
ESCA instrument PHI model 590 A, has revealed the presence of Zn, Ni, O, P and
traces of S.
The composition profile as a function of the sputtering time is shown in fig. 9.
The sputter etching was done using a differentially pumped ion gun with Ar ions
(beam voltage=5 kV, ion current density=l.53 x 10 -4 A/cm 2 and raster area
=2 x 2 mm 2 which corresponds to a precalibrated etching rate of 65 ,~ per minute of
Ta205). The depth profiling was started after sputter cleaning for about 40 s. The
quantity of P and S present being extremely small, we had to use a higher amplifica-
tion ( x 10) for detecting the peak to peak height. This incorporated a lot of noise
in the P and S profiles and their profiles in fig. 9 thus include the noise factor along
with their actual concentrations. After sputtering the film for 3 min, the P and S
profiles saturate to a constant level. This level may be considered as the noise level
since the Auger spot analysis done after sputtering failed to detect the presence of P
and S.
From the ESCA (using an Mg anode with input energy of 400 W) and the trans-
mission electron diffraction patterns taken at different spots of the film and identified
by reference to the standard data for Ni, NiO, Ni203, P(Orth) P(black), NivP 3, Zn
and Ni-Zn alloys, we have concluded that : (i) zinc is not present in any of its com-
pound forms. The binding energies of Zn 2p1~2 and Zn 2p3/2 ESCA peaks coincide
with those of elemental zinc [8]. However this does not exclude the possibility of its
existence as an alloy with nickel since the peak shift in core binding energies of zinc
and nickel would be negligible and difficult to detect. The electron diffraction patterns
530 S.N. Kumar el al. Eleclroh's.s" nickel black coatiH~l~

Zn

t RELATIVE GAIN
0 0 Znxl
U.I
"-I-
N[ x l
) 0 x 2
v

laJ P x 10
0.
S xlO
0
t.-

bJ
0..
IZ
laJ
(.9
<[

Ni

I I I i t I I I I 1 A 1
3 6 9 12
SPUTTERING TIME,MIN. °
Fig. 9, Sputter Auger depth profile of the etectroless nickel black coating.

suggest the possible existence of a Ni-Zn alloy. (ii) Nickel is present in its elemental
as well as in its combined states, namely, the two oxides, NiO and Ni20 3. The presence
of both NiO and Ni20 3 was strongly supported by the electron diffraction patterns.
The existence of nickel as elemental Ni, NiO and Ni20 3 has also been supported by
the ESCA of the corresponding 2p3/2 peaks. Qualitatively, Ni gives the strongest
peak followed by the Ni20 3 and NiO peaks. (iii) Phosphorous, present in a small
amount possibly exists in a combined state as there was a shift of 0.6 eV in the P 2p
peak. The electron diffraction pattern (fig. 10) gave strong evidence of the existence
of a phosphide, NiTP 3.
The relative amounts of total nickel and zinc were determined by Auger analysis
by comparing the peak-to-peak heights of Ni and Zn in the dN/dE versus E spectrum
and taking the elemental sensitivity factors [9]. The Ni to Zn ratio after sputter
cleaning for 40 s has been found to be 1 : 1.42. Detailed quantitative analysis of the
relative amounts of NiO and Ni20 3 is being done and will be communicated later.

4. Conclusions

The coating contains elemental nickel and zinc alongwith the oxides, NiO and
Ni203 and the phosphide, NiTP 3. Detailed quantitative analysis of the film phase
composition is required to investigate the physical mechanisms operating in these
films; this is being done presently and will be communicated later. Some of the
collector panels with these coatings, covered with a single glass cover, and exposed
to the atmosphere for more than nine months, have shown some white spots at the
 S. N. Kumar et al. / Electroless nickel black coatings 531

Fig. 10. Typical electron diffraction pattern of the coating showing the rings of Ni, Ni203, NivP3, Zn
and N~Zn alloy.

corners. It is hoped that, because of its simplicity and being economically viable,
electroless nickel black would prove to be a successful alternative to the black nickel
coatings prepared by electroplating and other techniques.

Acknowledgements

One of us (LKM) wishes to thank Prof. F. Abeles, J. Lafait and J. Behaghel of the
Laboratoire d'Optique des Solides, Paris for help in the optical measurements.
Thanks are due also to Dr. A. Banerjee and Mr. S. Rajagopalan for their help in the
SAM/ESCA measurements.

References

[1] B. O. Seral~hin, in: Topics in Applied Physics, Vol. 31, ed. B. O. Seraphin (Springer-Verlag, Berlin,
1979) p. 5.
532 S. N. K u m a r et al. ' Electroless nickel black coatin#.s

12] A. J. Sievers, in: Topics in Applied Physics, Vol. 3l, ed. B. O. Seraphin (Springer-Verlag, Berlin,
1979) p. 57.
[3] R. E. Hahn and B. O. Seraphim in: Physics of Thin Films, Vol. 10, eds. Georg Hass and Maurice H.
Francombe {Academic Press, New York, 1978) p. 1.
[4] Carl M. Lampert, Solar Energy Mater. 1 (1979) 319.
[5] J. M. Behaghel, S. Berthier, J. Lafait and J. Rivory, Solar Energy Mater. 1 (1979) 201.
[6] R. Blickensdefer, R. L. Lincoln and D. K. Deardroff, Albany Metallurgy Research Center, Albany,
Oreg. Bureau of Mines Report of Investigations 1976, United States Department of the Interior,
report no. 8167.
[7] M. P. Thekaekara, Data on incident Solar Energy NASA/Goddard Space Flight Center, Greenbelt,
MD.
[8] C. D. Wagner et al., in: Handbook of X-ray Photoelectron Spectroscopy, ed. G. E. Muilenberg
(Perki~Elmer Corporation, 1979).
[91 L. E. Davis et al., in: Handbook of Auger Electron Spectroscopy (Physical Electronics Industries.
Inc., 19761 p. 11.