METHOD FOR POST-TREATING AN ABSORBER LAYER

20220037553 · 2022-02-03

    Inventors

    Cpc classification

    International classification

    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:

    [0067] FIG. 1 diagrams showing relative solar parameters for solar cells with different Zn(O,S) buffer layers without post-treatment of the absorber layer according to the invention;

    [0068] FIG. 2 diagrams showing relative solar parameters for solar cells with differently post-treated absorber layers with Zn(O,S) buffer, with and without rinsing of the absorber layer;

    [0069] FIG. 3 a diagram showing the change in the mean charge carrier service life after application of the Zn(O,S) buffer layer on the absorber layer for various Na amounts and various post-treatment temperatures;

    [0070] FIG. 4 diagrams showing relative solar parameters for solar cells with differently post-treated absorber layers with Zn(O,S) buffer for various Na amounts and various post-treatment temperatures;

    [0071] FIG. 5 a diagram showing the relative efficiency of solar cells as a function of the Na amount for various post-treatment temperatures as well as with and without rinsing of the absorber layer;

    [0072] FIG. 6 diagrams showing relative secondary solar parameters (saturation current density JO and diode ideality factor n) for solar cells with Zn(O,S) buffer without and with post-treatment of the absorber layer according to the invention for various Na amounts and various post-treatment temperatures;

    [0073] FIG. 7 a diagram showing TOF-SIMS Na profiles of the buffer layer and absorber layer without and with post-treatment of the absorber layer according to the invention for various Na amounts and various post-treatment temperatures;

    [0074] FIG. 8 a diagram showing a surface S-correlated Raman signal for CIGSSe absorber surfaces without surface cleaning;

    [0075] FIG. 9 a diagram showing a CIG-correlated Raman signal for CIGSSe absorber surfaces without surface cleaning;

    [0076] FIG. 10 a diagram showing a reflectometry evaluation for CIGSSe absorber surfaces without surface cleaning;

    [0077] FIG. 11 a diagram showing a surface S-correlated Raman signal for CIGSSe absorber surfaces with surface cleaning;

    [0078] FIG. 12 a diagram showing a CIG-correlated Raman signal for CIGSSe absorber surfaces with surface cleaning;

    [0079] FIG. 13 a diagram showing a reflectometry evaluation for CIGSSe absorber surfaces with surface cleaning;

    [0080] FIG. 14 a flowchart to illustrate the steps of the method according to the invention for post-treating an absorber layer;

    [0081] FIG. 15 a flowchart to illustrate the steps of the method according to the invention for producing a layer system for the production of thin-film solar cells, wherein a post-treatment of the absorber layer according to the invention is done.

    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 FIG. 1, which describes the prior art. Previously, it has been shown that the efficiency of thin-film solar cells with a Zn(O,S) buffer layer is always lower than that of cells with a In.sub.xS.sub.y buffer layer. With the objective of avoiding this reduction in efficiency, three different S/(S+O) ratios of the Zn(O,S) buffer layer were tested in FIG. 1.

    [0085] FIG. 1 shows, with four diagrams, the relative solar parameters of relative efficiency Eta, relative open clamping voltage Voc, relative short-circuit current density Jsc, and relative fill factor FF of solar cells with different Zn(O,S) buffer layers, in each case based on a Na-doped InS buffer layer. The Cu(In,Ga)(S,Se).sub.2 absorber layer was not subjected to any post-treatment according to the invention. The Zn(O,S) buffer layers were differentiated by the different S/(S+O) proportions, with the proportion of S/(S+O) increasing from left to right. The values for the solar parameters of the solar cell with the Na-doped In.sub.xS.sub.y buffer layer served as a reference and are plotted in each diagram as a horizontal line.

    [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 FIG. 2. FIG. 2 shows, analogously to FIG. 1, the relative solar parameters of relative efficiency Eta, relative open clamping voltage Voc, relative short-circuit current density Jsc, and relative fill factor FF for solar cells with differently post-treated absorber layers with Zn(O,S) buffer, wherein the absorber layer was subjected to a post-treatment according to the invention, in each case based on a Zn(O,S) buffer layer that was applied on an absorber layer that was not post-treated. The sub-diagrams on the left refer in each case to the Zn(O,S) buffer layer on a non-treated absorber layer. The center sub-diagrams refer to Zn(O,S) buffer layers, wherein the surface of the absorber layer was subjected to surface cleaning after the diffusion of the sodium sulfide and before the application of the respective Zn(O,S) buffer layer. Three differently post-treated absorber layers with different Na content are shown, with the Na content increasing from left to right (Na-3>Na-2>Na-1). The sub-diagrams on the right refer to differently post-treated absorber layers with Zn(O,S) buffer, wherein the surfaces of the absorber layers were not cleaned before the application of the respective Zn(O,S) buffer layer. For this case, two differently post-treated absorber layers with different Na content are shown in each case, with the Na content increasing from left to right (Na-2>Na-1).

    [0088] FIG. 2 shows that for the smallest amount of sodium (Na-1) in both cases (with and without rinsing of the absorber layer), a slight decrease in efficiency occurs in each case compared to the absorber layer without post-treatment. Only with a larger amount of sodium is the advantageous effect on the efficiency Eta, as well as the open clamping voltage Voc and the fill factor FF seen. A further improvement of the solar parameters can be achieved by cleaning the surface of the absorber layer. When the surface of the absorber layer is not cleaned, there is already a decrease in the fill factor FF with the use of a moderate amount of sodium (Na-2).

    [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. FIG. 3 shows a diagram, in which the change in the mean charge carrier service life after application of the Zn(O,S) buffer layer on the absorber layer is shown for three different Na amounts Na-1 (second sub-diagram from the left), Na-2 (third sub-diagram from the left), and Na-3 (fourth sub-diagram from the left), based in each case on the mean charge carrier service life of the layer system without a buffer layer (absorber layer+back electrode layer+carrier). As a reference, the mean charge carrier service life of the layer system with a buffer layer, but without post-treatment of the absorber layer according to the invention is indicated (first sub-diagram on the left). The Na amount increases from left to right, i.e., Na-3>Na-2>Na-1. For each Na amount, the diffusion of the post-treatment material was carried out at two different (furnace) temperatures Temp-1, Temp-2, where Temp-2>Temp-1. The surface of the absorber layer was cleaned, before the Zn(O,S) buffer layer was applied.

    [0090] FIG. 3 shows that the change in the mean charge carrier service life without post-treatment according to the invention is negative, in other words, the mean charge carrier service life is reduced after application of the Zn(O,S) buffer, whereas the change in the mean charge carrier service life with post-treatment according to the invention is positive, in other words, the mean charge carrier service life is increased after application of the Zn(O,S) buffer on the post-treated absorber layer. With the same amount of Na in each case, with post-treatment of the absorber layer according to the invention, an increase in the change in the charge carrier service life occurs with an increase in the temperature with the tempering of the the post-treatment material.

    [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. FIG. 4 shows the relative solar parameters of relative efficiency Eta, relative open clamping voltage Voc, relative short-circuit current density Jsc, and relative fill factor FF for solar cells with differently post-treated absorber layers with Zn(O,S) buffer, based in each case on a solar cell with Zn(O,S) buffer, which is applied on an absorber layer not post-treated according to the invention. The left sub-diagrams refer in each case to a Zn(O,S) buffer layer that was applied on a non-post-treated absorber layer. The center sub-diagrams refer to Zn(O,S) buffer layers, wherein the surface of the absorber layer was subjected to surface cleaning after the diffusion of the sodium sulfide and before the application of the respective Zn(O,S) buffer layer. Three differently post-treated absorber layers with Zn(O,S) buffer with different Na content (originating from the sodium sulfide) are shown, wherein the Na content increases from left to right (Na-3>Na-2>Na-1). In the center sub-diagrams, the post-treatment of the absorber layer was carried out at a temperature Temp-1. The right sub-diagrams refer to Zn(O,S) buffer layers, wherein the surface of the absorber layer was subjected to cleaning after the diffusion of sodium sulfide and before the application of the respective Zn(O,S) buffer layer. Three differently post-treated absorber layers with different Na content are shown, wherein the Na content increases from left to right (Na-3>Na-2>Na-1). In the right sub-diagrams, the post-treatment of the absorber layer was carried out at a temperature Temp-2, where Temp-2>Temp-1.

    [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.

    [0093] FIG. 5 shows the influence of the Na amount on the relative efficiency Eta. Various measured values are shown for a solar cell with a Zn(O,S) buffer layer that was applied on an absorber layer post-treated according to the invention, wherein the absorber layer had been cleaned or had not been cleaned before the application. Serving as a reference (horizontal line for relative efficiency rel. Eta=1) was a solar cell with a Zn(O,S) buffer layer that had been applied on an absorber layer not post-treated according to the invention, wherein the absorber layer was cleaned in the same manner before the application of the Zn(O,S) buffer layer. As shown in FIG. 5, an improvement in efficiency can already be achieved with an alkali amount of at least 0.02 at. % in the absorber layer.

    [0094] FIG. 6 shows relative secondary solar parameters (saturation current density JO and diode ideality factor n) for solar cells with Zn(O,S) buffer without post-treatment according to the invention and with post-treatment of the absorber layer according to the invention for various Na amounts, as well as three different post-treatment temperatures Temp-1, Temp-2, and Temp-3, where Temp-3>Temp-2>Temp-1. The surface of the absorber layer was cleaned in each case before deposition of the Zn(O,S) buffer layers. Saturation current density and diode ideality factor were obtained by modeling the measured I-V characteristic curve according to the one-diode model. High values of these secondary solar parameters indicate increased recombination in the region of the absorber/buffer junction. As a result of the post-treatment of the absorber layer according to the invention, the recombination of the charge carriers in the region of the absorber/buffer junction is significantly reduced.

    [0095] FIG. 7 shows TOF-SIMS Na profiles of the buffer layer and the absorber layer without post-treatment of the absorber layer according to the invention and with post-treatment of the absorber layer according to the invention for two different Na amounts N-1 and Na-2, where Na-2>Na-1, and for two different post-treatment temperatures Temp-1 and Temp-2, where Temp-2>Temp-1. The signal intensity is plotted against the sputtering time.

    [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] FIG. 8 shows the surface S-correlated Raman signal for CIGSSe absorber surfaces. “Stage 1” refers to the state before the post-treatment according to the invention; “Stage 2”, to the state after the post-treatment according to the invention or after the tempering of the absorber layer. The measurement points for Stage 1 are marked with “SI”; the measurement points for Stage 2, with “S2”.

    [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] FIG. 9 shows the CIG-correlated Raman signal for CIGSSe absorber surfaces. “Stage 1” refers to the state before the post-treatment according to the invention; “Stage 2”, to the state after post-treatment according to the invention or after tempering. The measurement points for Stage 1 are marked with “S1”; the measurement points for Stage 2, with “S2”.

    [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.

    [0102] FIG. 10 shows a reflectometry evaluation for CIGSSe absorber surfaces. “E1” corresponds to a peak in the reflection spectrum that correlates with the surface band gap determined by the S/Se content in these absorbers. “Egap” corresponds to the minimum band gap in the absorber depth. “Stage 1” refers to the state before the post-treatment according to the invention; “Stage 2”, to the state after post-treatment according to the invention or after tempering. The measurement points for Stage 1 are marked with “S1”; the measurement points for Stage 2, with “S2”.

    [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.

    [0105] FIG. 11 shows the surface S-correlated Raman signal for CIGSSe absorber surfaces. “Stage 1” refers to the state before the post-treatment according to the invention; “Stage 2”, to the state after post-treatment according to the invention or after tempering; “Stage 3”, to the state after alkali sulfide post-treatment or after tempering and an additional cleaning step of the absorber surface. The measurement points for Stage 1 are marked with “S1”; the measurement points for Stage 2, with “S2”; the measurement points for Stage 3, with “S3”.

    [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.

    [0107] FIG. 12 shows the CIG-correlated Raman signal for CIGSSe absorber surfaces. “Stage 1” refers to the state before the post-treatment according to the invention; “Stage 2”, to the state after post-treatment according to the invention or after tempering; “Stage 3”, to the state after alkali sulfide post-treatment or after tempering and an additional cleaning step of the absorber surface. The measurement points for Stage 1 are marked with “S1”; the measurement points for Stage 2, with “S2”; the measurement points for Stage 3, with “S3”.

    [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.

    [0109] FIG. 13 shows a reflectometry evaluation for CIGSSe absorber surfaces. “E1” corresponds to a peak in the reflection spectrum that correlates with the surface band gap determined by the S/Se content in these absorbers. “Egap” corresponds to the minimum band gap in the absorber depth. “Stage 1” refers to the state before the post-treatment according to the invention; “Stage 2”, to the state after post-treatment according to the invention or after tempering; “Stage 3”, to the state after alkali sulfide post-treatment or after tempering and an additional cleaning step of the absorber surface. The measurement points for Stage 1 are marked with “S1”; the measurement points for Stage 2, with “S2”; the measurement points for Stage 3, with “S3”.

    [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.

    [0112] FIG. 14 schematically illustrates, with reference to a flowchart, the method for post-treating an absorber layer of a layer system for the production of thin-film solar cells. First, in a first step I, a chalcogen-containing absorber layer on a carrier is provided. Next, in a second step II, a post-treatment layer is applied 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. Then, in a third step III the at least one post-treatment material is thermally diffused into the absorber layer. Preferably, in an optional fourth step IV, the absorber surface is cleaned.

    [0113] FIG. 15 schematically illustrates, with reference to a flowchart, the method for producing a layer system for the production of thin-film solar cells, in which the absorber layer is post-treated according to the invention. First, in a first step I, a carrier is provided. In a second step II, a back electrode layer is produced on the carrier. In a third step III, a chalcogen-containing absorber layer is produced on the back electrode layer. In a fourth step IV, a post-treatment layer is applied 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. Then, in a fifth step V, the at least one post-treatment material is thermally diffused into the absorber layer. In a sixth step VI, at least one buffer layer is produced on the absorber layer. Finally, in a seventh step VII, a front electrode layer is produced on the buffer layer. Preferably, in an optional step, the absorber surface is cleaned after the diffusion of the at least one post-treatment material and before the application of the buffer layer on the absorber layer.

    [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.