METHOD FOR POST-TREATING AN ABSORBER LAYER
20220037553 · 2022-02-03
Inventors
Cpc classification
H01L31/0324
ELECTRICITY
H01L31/055
ELECTRICITY
Y02E10/541
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E10/52
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01L31/0468
ELECTRICITY
H01L31/186
ELECTRICITY
International classification
H01L31/18
ELECTRICITY
H01L31/032
ELECTRICITY
H01L31/0468
ELECTRICITY
Abstract
A method for post-treating an absorber layer for photoelectric conversion of incident light into electric current. The method includes providing a chalcogen-containing absorber layer on a carrier, applying a post-treatment layer on a surface of the absorber layer, wherein the post-treatment material is not a buffer or component of a buffer, and thermally diffusing the post-treatment material into the absorber layer. A method for producing a layer system for the production of thin-film solar cells is also described.
Claims
1.-15. (canceled)
16. A method for post-treating an absorber layer for photoelectric conversion of incident light into electric current, comprising: providing a chalcogen-containing absorber layer on a carrier; applying a post-treatment layer on a surface of the absorber layer, wherein the post-treatment layer contains at least one post-treatment material selected from the group consisting of a metal chalcogenide, an oxygen compound of a metal chalcogenide, and a hydrogen-oxygen compound of a metal chalcogenide; and thermally diffusing the at least one post-treatment material into the absorber layer.
17. The method according to claim 16, wherein the post-treatment material is selected from the group consisting of an alkali sulfide, an alkaline earth sulfide, a hydrogen-oxygen compound of a metal chalcogenide with oxidation state IV, an oxygen compound of a metal chalcogenide with oxidation state IV, a hydrogen-oxygen compound of a metal chalcogenide with oxidation state VI, and an oxygen compound of a metal chalcogenide with the oxidation state VI.
18. The method according to claim 17, wherein the alkali sulfide is selected from the group consisting of Na.sub.2S, K.sub.2S, Rb.sub.2S and Cs.sub.2S; the alkaline earth sulfide is selected from the group consisting of MgS, and CaS; the hydrogen-oxygen compound of a metal chalcogenide with oxidation state IV is selected from the group consisting of NaHSO.sub.3, KHSO.sub.3, RbHSO.sub.3, and CsHSO.sub.3; the oxygen compound of a metal chalcogenide with oxidation state IV is selected from the group consisting of Na.sub.2SO.sub.3, K.sub.2SO.sub.3, Rb.sub.2SO.sub.3, and Cs.sub.2SO.sub.3; the hydrogen-oxygen compound of a metal chalcogenide with oxidation state VI is selected from the group consisting of NaHSO.sub.4, KHSO.sub.4, RbHSO.sub.4, and CsHSO.sub.4; and the oxygen compound of a metal chalcogenide with oxidation state VI is selected from the group consisting of Na.sub.2SO.sub.4, K.sub.2SO.sub.4, Rb.sub.2SO.sub.4, Cs.sub.2SO.sub.4.
19. The method according to claim 16, wherein the absorber layer has, after the thermally diffusing, a metal content in a range from 0.02 atomic % to 2.5 atomic %, based on a total amount of material of the absorber layer.
20. The method according to claim 19, wherein the range is from 0.1 atomic % to 1.3 atomic %.
21. The method according to claim 16, wherein the post-treatment layer contains exactly one post-treatment material selected from the group consisting of exactly one alkali chalcogenide, exactly one oxygen compound of an alkali chalcogenides, and exactly one hydrogen-oxygen compound of an alkali chalcogenide, wherein only one single alkali element is chemically bound in the post-treatment material.
22. The method according to claim 16, wherein the at least one post-treatment material is applied on the surface of the absorber layer by a process selected from thermal evaporation, wet-chemical bath deposition, electron beam evaporation, sputtering, atomic layer deposition, and spray pyrolysis.
23. The method according to claim 16, wherein the thermally diffusing comprises heating the post-treatment layer.
24. The method according to claim 23, wherein the heating occurs in a temperature range from 70° C. to 700° C. with a heating time in a range from 1 min to 120 min.
25. The method according to claim 24, wherein the temperature range is from 150° C. to 700° C.
26. The method according to claim 23, wherein the heating occurs with an energy input in a range from 0.5 J/cm.sup.2 to 15 J/cm.sup.2.
27. The method of claim 26, wherein the energy input is made of pulses with a pulse duration in a range from 0.2 msec to 20 msec.
28. The method according to claim 16, wherein the absorber layer has a temperature in a range from 300° C. to 800° C. during application of the post-treatment layer.
29. The method according to claim 16, wherein the thermally diffusing the at least one post-treatment material into the absorber layer is performed in a vacuumed environment.
30. The method according to claim 16, wherein the thermally diffusing the at least one post-treatment material into the absorber layer is performed in an atmosphere containing at least one chalcogen or in a chalcogen-free atmosphere.
31. The method according to claim 30, wherein the chalcogen-free atmosphere consists of inert gas.
32. The method according to claim 16, further comprising removing the at least one post-treatment material from the surface of the absorber layer after the thermally diffusing.
33. A method for producing a layer system for production of thin-film solar cells, comprising: providing a carrier; producing a back electrode layer on the carrier; producing a chalcogen-containing absorber layer on the back electrode layer, the chalcogen-containing absorber layer being treated according to the method of claim 16; depositing at least one buffer layer on the chalcogen-containing absorber layer; and producing a front electrode layer on the at least one buffer layer.
34. The method according to claim 33, wherein the at least one buffer layer is deposited in a vacuumed environment.
35. The method according to claim 34, wherein the at least one buffer layer is deposited by sputtering.
36. A thin-film solar cell production method, comprising: producing a layer system for thin-film solar cells, wherein the producing comprises the method of claim 16.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0066] The invention is now explained in detail with reference to the accompanying figures. They depict:
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DETAILED DESCRIPTION OF THE DRAWINGS
[0082] For the tests described below, the results of which are presented in diagrams, thin-film solar cells or thin-film solar modules that are based on a layer system with the following layers were produced:
[0083] A back electrode layer made of molybdenum (Mo) was applied on a carrier made of glass. A CIGSSe absorber layer was produced on the back electrode layer (by deposition of a precursor layer, containing copper, indium, gallium, Se and thermal conversion of the precursor layer in an RTP process to form the compound semiconductor in an S-containing atmosphere). A buffer layer was deposited on the CIGSSe absorber layer. In the layer systems for post-treatment according to the present invention (FIG. en to 13), a zinc oxysulfide buffer layer, abbreviated Zn(O,S), in particular a mixture of ZnO/ZnS, deposited by sputtering on the CIGSSe absorber layer, was used. A front electrode layer of aluminum-doped zinc oxide (ZnO) was deposited on the buffer layer. Used for post-treatment of the CIGSSe absorber layer was a metal chalcogenide, specifically an alkali sulfide (here, for example, sodium sulfide, Na.sub.2S), that had been deposited on the CIGSSe absorber layer after its crystallization. The diffusion of the sodium sulfide into the CIGSSe absorber layer was done in a furnace at a temperature in the range of 300°, wherein the carrier glass was in thermal equilibrium with the post-treatment layer. Optionally, the surface of the CIGSSe absorber layer was cleaned before the deposition of the buffer layer (here, for example, by rinsing with deionized water).
[0084] Consider first
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[0086] As can be seen from the diagrams, the efficiency Eta and the open clamping voltage Voc for the solar cells with the Zn(O,S) buffer layer are lower for all S/(S+O) ratios than the corresponding solar parameters for the solar cell with the Na-doped InS buffer layer. With the highest value or the mean value of the S/(S+O) ratio of the Zn(O,S) buffer layer, an approx, equal value for the corresponding solar parameters of the solar cell with the Na-doped InS buffer layer can be achieved in each case for the short-circuit current density Jsc or the fill factor FF. As a result, it should be noted that even by changing the S/(S+O) ratio of the Zn(O,S) buffer layer, no sufficient improvement of the solar parameters can be achieved.
[0087] The effect of the post-treatment of the absorber layer according to the invention with and without rinsing of the absorber layer before deposition of the buffer layer is discernible from
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[0089] The effect of the post-treatment according to the invention in the absorber layer or at the buffer layer/absorber layer interface can even be determined directly in a change in the mean charge carrier service life from a time-dependent photoluminescence measurement with and without post-treatment of the absorber layer according to the invention.
[0090]
[0091] The achievable efficiency is a function of the alkali amount and the temperature of the post-treatment layer at the time of diffusion of the post-treatment material into the absorber layer.
[0092] The improvement of the efficiency of a solar cell with a Zn(O,S) buffer layer through the post-treatment of the absorber layer according to the invention exhibits both a dependence on the alkali amount and the temperature used during the post-treatment (carrier temperature, furnace temperature). No saturation of the effect of the post-treatment is discernible; an increase in temperature with an increase in the Na amount appears particularly advantageous.
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[0096] Accordingly, there is an increase in the Na amount in the buffer layer/absorber layer interface region with increasing Na amount and/or temperature, which extends far into the absorber depth. Also, at the transition of the CIGSSe absorber layer to the molybdenum-based back contact, there is an increase in the Na signals in TOF-SIMS compared to the reference layer; however, here, the incorporation seems to be driven more by solubility of the sodium in the layers involved since there is little dependence on the Na amount and/or the temperature of the post-treatment of the absorber layer.
[0097] The absorber layer has, after application and tempering of the post-treatment material, without cleaning of the absorber surface, various additional properties.
[0098]
[0099] Accordingly, the surface S-correlated Raman signal for the absorber layer with alkali sulfide application and tempering shows a significant increase of 13%_rel in comparison with an absorber layer without alkali sulfide tempered in a comparable atmosphere (vacuum), which loses 20%_rel of the Raman signal, in each case relative to the signal intensity of the absorber surface before post-treatment according to the invention or tempering.
[0100]
[0101] Accordingly, the surface CIG-ratio-correlated Raman signal for the absorber layer with alkali sulfide post-treatment shows less change than for the tempered-only absorber layer. An increase in the Raman signal would be an indication of an increase in the surface Cu/In+Ga (CIG) ratio.
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[0103] Accordingly, the E1 signal from the reflectometry (correlation with the surface band gap of the absorber) for the absorber with alkali sulfide post-treatment shows a significant reduction of the surface band gap, whereas the the tempered-only absorber has an unchanged surface band gap, relative in each case to the state before post-treatment or tempering.
[0104] After application and tempering of the post-treatment material, after the additional cleaning step of the absorber surface, e.g., by rinsing, the absorber layer has various additional properties.
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[0106] Accordingly, the surface S-correlated Raman signal for the absorber with alkali sulfide application and tempering shows, even after the cleaning step of the absorber surface, an increase compared to an absorber without alkali sulfide tempered in a comparable atmosphere (vacuum), relative in each case to the signal intensity of the absorber surface before post-treatment or tempering.
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[0108] Accordingly, the surface CIG-ratio-correlated Raman signal shows, after the additional cleaning step of the absorber surface, no change for the absorber with the alkali sulfide post-treatment; in the case of the tempered-only absorber, a slight decrease in the Raman signal is to be noted. Overall, for the absorber with alkali sulfide post-treatment, the surface CIG ratio does not differ from that with the tempered-only absorber.
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[0110] Accordingly, the E1 signal from the reflectometry (correlation with the surface band gap of the absorber) for the absorber with alkali sulfide post-treatment shows a significant increase in the surface band gap only as a result of the additional cleaning step of the absorber surface, whereas the tempered-only absorber has an unchanged surface band gap even after the cleaning step, relative in each case to the state before post-treatment or tempering.
[0111] In the case of the sulfoselenide surface of the sequential absorber, it is only through the use according to the invention of an S-containing post-treatment material that S-depletion of the absorber surface can be prevented in the post-treatment process. Analogously, it can be concluded from this that in the case of an absorber with a purely selenide surface, an Se-containing post-treatment material must be used to prevent Se-depletion of the absorber surface in the post-treatment process.
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[0114] It follows from the above statements that through the post-treatment of the absorber layer according to the invention, an improvement of the solar module parameters, in particular of the efficiency, of thin-film solar modules can advantageously be achieved. The post-treatment material has a dual function and serves simultaneously as a supplier of the alkali metal for alkali passivation of the absorber layer and also as a supplier of the chalcogen for surface termination of the absorber layer, in particular of Se for purely selenide co-evaporation absorbers and S for mixed sulfo-selenide sequential absorbers. The post-treated absorber layer makes the use of buffer layers based on Zn(O,S) economically viable and enables, in particular, the use of a vacuum method for the deposition of the buffer layer. This significantly facilitates the production of the buffer layer and reduces the costs of production of the layer system. Moreover, ecological advantages are achieved.