KR20150032858A - Use of microporous anionic inorganic framework structures containing dopant cations for producing thin film solar cells - Google Patents

Abstract

The present invention relates to a semiconductor light absorbing layer of a thin film solar cell and / or a thin film solar module for absorbing impurities from thin film solar cells and / or thin film solar modules, And more particularly, to the use of microporous anionic inorganic framework structures, particularly skeletal silicates or skeletal germanium salts, in thin film solar cells or thin film solar modules based on an organic substrate layer for producing the provided semiconductor light absorbing layer . The present invention also relates to a photovoltaic thin film solar cell comprising at least one back electrode layer, at least one contact layer, and / or one or more semiconductor light absorbing layers, comprising microporous anionic inorganic skeletal structures, particularly skeletal silicates or skeletal germanates, . In this case, preferably, the semiconductor light absorbing layer is doped with monovalent dopant cations, especially alkali ions, which are initially produced from the skeleton structures, in particular in exchange with the metal ions of the semiconductor light absorbing layer. In addition, the present invention relates to a thin film solar module comprising the thin film solar cells according to the present invention. Finally, the present invention relates to a thin film solar cell and a method for manufacturing thin film solar modules according to the present invention.

Description

USE OF MICROPOROUS ANIONIC INORGANIC FRAMEWORK STRUCTURES CONTAINING DOPANT CAPTURE FOR PRODUCING THIN FILM SOLAR CELLS FOR PREPARING THIN FILM SOLAR CELL,

The present invention relates to the use of microporous anionic inorganic framework structures, particularly those containing dopant cations, for the production of thin film solar cells and / or thin film solar modules, and to the use of photovoltaic thin film solar cells and photoelectric cells comprising microporous anionic inorganic framework structures Thin-film solar modules, and methods for making the thin-film solar modules.

Solar photovoltaic modules have long been known and commercially available. Suitable solar modules include on one hand a crystalline silicon solar module and on the other hand a so-called thin film solar module. Thin-film solar modules of this type form a complex multi-layer system based on the use of, for example, so-called chromium semiconductor light absorbing layers, such as Cu (In, Ga) (Se, S) ₂ - system. In the case of the thin film solar modules, a molybdenum back electrode layer is typically placed on the glass substrate. Such a molybdenum backside electrode layer comprises a precursor metal thin film comprising copper and indium and optionally gallium in the process variant and then converted into the so-called CIS to CIGS system when the temperature rises in the presence of hydrogen sulphide and / or hydrogen selenide do. In a further process variation, elemental selenium vapors and sulfur vapors may be used instead of hydrogen selenide and hydrogen sulphide. As a result, the fabrication of the thin film solar modules is a multi-step process in which each method step due to numerous interactions has to be adjusted to suit closely followed method steps. In addition, special attention is also required for the selection of the materials to be used for each layer and for their purity. This also applies to the substrate layer itself. In a wide variety of process steps, each impurity can continually degrade efficiency. This requires always the use of high purity starting materials and high equipment cost. This generally involves significant cost. Also, until now, at the temperature and reaction conditions applied in the individual fabrication steps, contamination or internal diffusion of the components, dopants or impurities of the individual layers of the multi-layer system could not be ruled out. Already the choice of the fabrication of the back electrode layer and its type, can affect the efficiency of thin film solar cells. For example, the back electrode layer has a high lateral conductivity to ensure a low-loss series connection. In addition, the substances which move to the outside of the substrate and / or the semiconductor light absorbing layer should not affect the quality and function of the back electrode layer or the semiconductor light absorbing layer. In addition, the material of the back electrode layer should have good adaptability to the thermal expansion behavior of the substrate and the layers deposited thereon to prevent microcracking. Also, the adhesion on the substrate surface must meet all common usage requirements. Finally, when efficiency improvement is to be achieved through particularly suitable dopants, care should be taken to the uniformity of the composition of the individual layers of the thin film system.

Though excellent efficiency can be achieved through the use of highly pure back electrode materials, this always entails overly high production costs. In addition, the aforementioned migration phenomena, especially diffusion phenomena, often cause significant contamination of the back electrode material under normal production conditions. For example, the dopant introduced into the semiconductor light absorbing layer diffuses into the back electrode through the above-mentioned diffusion, and as a result, it can be depleted in the semiconductor light absorbing layer. As a result, the finished solar module has much lower efficiency. Thus, despite all the optimization of methods and materials, there is always still a strong limit to the final design of the thin-film solar modules offered for sale.

According to DE 44 42 824 C1, a chromium semiconductor light absorbing layer is doped with one element selected from the group of sodium, potassium and lithium at a dose of 10 ¹⁴ to 10 ¹⁶ atoms / cm 2, and at the same time, By providing a diffusion barrier layer, it is possible to obtain a photovoltaic layer suitably formed in a morphology and a solar cell having excellent efficiency.

As an alternative, it is proposed to use a non-alkali substrate when the diffusion barrier layer should be omitted.

Likewise, the sodium ion diffused from the substrate glass under the temperature given when the semiconductor light absorbing layer is produced can be used without processing the barrier layer. However, such measures are not very reliable and do not allow the desired sodium doping of the semiconductor light absorbing layer. In general, it can be adhered to in this way that the amount of sodium ions diffusing from the substrate glass is set only with difficulty. The diffusion of sodium ions is influenced not only by the glass itself and the storage and pretreatment of the glass but also by the back electrode layer present between the substrate layer and the semiconductor light absorbing layer and in this case the additional layers. For example, the lateral non-uniformity of the back electrode layer causes non-uniform diffusion of sodium ions into the semiconductor light absorbing layer.

Conversely, introduction of inorganic sodium compounds such as sodium fluoride, sodium sulfide, sodium selenide, or sodium phosphate may cause unintended defects in the semiconductor light absorbing layer, and / There is often a risk of being hygroscopic. For example, oxygen is known to generate electrical defects in the semiconductor light absorbing layer.

In addition, conventional introduction schemes of sodium ions in the semiconductor light absorbing layer have sometimes been found to be very inefficient. This is because only a very small amount of sodium ions normally introduced is actually included in the semiconductor light absorbing layer and electrically operated there.

In addition, it should not be underestimated that suitable sodium compounds, such as sodium fluoride, are difficult to handle and result in high manufacturing costs.

It would therefore be desirable to provide photovoltaic solar modules that no longer have the disadvantages of the prior art. It is therefore an object of the present invention to introduce dopant cations such as, for example, sodium ions in a suitably metered amount into a thin film solar module, especially a semiconductor light absorbing layer. It is also an object of the present invention to minimize or eliminate the negative effects of impurities on the efficiency of thin film solar cells. It is also an object of the present invention to provide a method for manufacturing thin film solar modules that does not have the disadvantages of the prior art. In this case, preferably, the dopant cations, especially the sodium ions, are particularly uniformly introduced into the semiconductor light absorbing layer in an appropriately metered and settable amount so as to reliably, efficiently, repeatably and / or electrically act Is provided. It is also an object of the present invention to provide a method for minimizing or eliminating adverse effects of impurities on the efficiency of thin film solar cells.

This object is achieved by the use of a microporous anionic inorganic skeleton structure, in particular comprising a dopant cation, for the production of thin film solar cells and / or thin film solar modules, according to the independent claims, and a photoelectric thin film comprising a microporous anionic inorganic skeleton structure A solar cell, and a method of manufacturing the solar cell module.

According to the present invention, the dopant cations are introduced into the thin film solar module, particularly the semiconductor light absorbing layer, in an appropriately metered amount. Further, according to the present invention, the negative influence of the impurities on the efficiency of the thin film solar cells is minimized or eliminated. In addition, the present invention provides a method for manufacturing thin film solar modules that minimizes or eliminates the adverse effects of impurities on the efficiency of thin film solar cells.

In accordance with the present invention, thin film solar cells or thin film solar modules or thin film solar modules based on an organic substrate layer, for example comprising a glass plate or in the form of a glass plate, for absorbing impurities from thin film solar cells and / It has been discovered that microporous anionic inorganic skeletal structures, particularly skeletal silicates or skeletal germanium salts, are used. The absorption of the impurities here can in particular be the absorption of impurities coming from the thin film solar cell, for example Fe ^{3 +} and / or Ni ^{2 +} .

In this case, in a suitable construction, the microporous anionic inorganic framework structures, in particular skeletal silicates or skeletal germanates, may be applied to one or more of the back electrode layers of the thin film solar cell or thin film solar module, the one or more contact layers, Lt; / RTI >

By means of the mentioned microporous anionic inorganic framework structures, it is possible to effectively and efficiently introduce impurities, such as water molecules, as well as iron and nickel ions, iron and nickel compounds, which are introduced during the course of successive process steps, Can be absorbed. These impurities can be inserted into the micropores of the framework structures, where they no longer have an adverse effect on efficiency. In this case, preferably, the skeletal structures mentioned are inert, that is to say they do not vary under the conditions of manufacture and use of the thin film solar modules, for example they are not degraded and do not participate in the reaction with other substances. Also, preferably, skeletal structures having various microporous diameter sizes can be used, and any impurities can be intentionally absorbed from the intermediate stages of the thin film solar cell or thin film solar cell through the microporous diameter sizes used Can be set. In this case, a porous skeleton having a very small diameter size of, for example, 0.29 nm or less, which can always absorb metal ions, may be used.

In a further preferred embodiment, the thin film solar cell or thin film solar module, in particular one or more semiconductor light absorbing layers of this thin film solar cell and / or thin film solar module, comprise monovalent dopant cations, especially alkali ions.

Furthermore, in order to produce the above-described semiconductor light absorbing layer in which a semiconductor light absorbing layer of a thin film solar cell and / or a thin film solar module based on a glass substrate layer including a glass plate or in the form of a glass plate and provided with monovalent dopant cations, It has been found to use microporous anionic inorganic framework structures, particularly skeletal silicates or skeletal germanates, containing monovalent dopant cations, especially alkali ions, in the pores.

In this case, in particular, it is possible, via outflow, from univalent dopant cations, in particular from alkali ions, into one or more rear electrode layers, one or more contact layers and / or one or more semiconductor light absorbing layers of the thin film solar cell and / The liberated microporous anionic inorganic framework structures, particularly skeletal silicates or skeletal germanates, can be present in one or more of the back electrode layers, one or more contact layers, and / or one or more semiconductor light absorbing layers of the thin film solar cell and / or thin film solar module have.

In addition, in order to dope the semiconductor light absorbing layer of the thin film solar cell and / or the thin film solar module with monovalent dopant cations, microporous anionic inorganic skeletal structures containing monovalent dopant cations, especially alkali ions, , In particular skeletal silicates or skeletal germanium salts.

The skeleton structures used in accordance with the present invention, which contain dopants or alkali ions within the micropores, may also be referred to as intercalation compounds.

The dopant cation in the sense of the present invention may mean a cation suitable for improving the electrical characteristics or efficiency of a thin film solar cell in particular. This is typically accomplished through absorption of the cations into the semiconductor light absorbing layer. In this case, the dopant cations reach through the microporous anionic inorganic framework structures, within the thin film solar cell as a medium or dopant, or within the components that form such a thin film solar cell. There, the dopant cations can move into the semiconductor light absorbing layer liberated through energy supply, such as heating and / or exchange with other materials, especially cations.

In a preferred configuration, the microporous anionic inorganic framework structures, particularly the skeletal silicates, may comprise tetrahedral structural units, or may be formed of these tetrahedral structural units.

Suitable skeletal silicates are, in particular, aluminoskeletal silicates, titanium aluminoskeletal silicates, boron skeletal silicates, gallo skeletal silicates, indium skeletal silicates, or ferro (III) -basic silicates.

In a particularly suitable configuration of the invention, the framework structure, in particular the skeletal silicate, comprises or consists of beta cages, in particular concentrated beta cages.

Thus, in the case of the framework structures used in accordance with the present invention, the existing cage structures can be composed of Al ^{3 +} ions, Si ^{4 +} ions, and O ^{2 -} ions, for example.

The skeletal structures used in accordance with the present invention, particularly skeletal silicates, are preferably skeletal silicates that are not hygroscopic.

In a particularly suitable configuration, the skeleton, especially the microporous of the skeleton silicate are, the metal ion of the metal of the semiconductor light absorption layer, for example, Cu ^+, Ga ^{3 +} and / or to In ^{3 +,} and / or impurities coming from the thin-film solar cell Such as Fe < ^{3 +} & gt ^; and / or Ni ^< ^{2 + &} gt ;, with a porous opening diameter allowing the exchange of dopant cations, especially alkali ions, in the micropores. Preferably said exchange is carried out at a temperature of at least 300 ° C, in particular in the range of from 350 ° C to 600 ° C, and preferably in the range of from 520 ° C to 600 ° C. In this case, preferably, when alkali ions are exchanged with ions from the semiconductor light absorbing layer as described above, the skeleton structure is not decomposed but generally maintained in a completely intact state. Such exchange of the ions at such an elevated temperature condition can be achieved not only when the skeleton structure including, for example, dopant cations, particularly alkali ions, is present in the semiconductor light absorbing layer itself, but also in the back electrode layer directly or indirectly adjacent to the semiconductor light absorbing layer . By the use according to the invention, all dopant cations or alkaline ions, especially sodium ions, present in the framework structure can be converted into cations from the semiconductor light absorbing layer and / or impurities in the thin film solar cell, such as iron and / or nickel Compounds to Fe ^{3 +} ions and / or Ni ^{2 +} ions.

Also preferred in this case are embodiments in which the framework structure, in particular the skeletal silicate, contains sodium ions, potassium ions, lithium ions, rubidium ions and / or cesium ions, in particular sodium ions, in the micropores .

Particularly suitable for the present invention are skeletons, particularly skeletal silicates, having micropores having a pore opening diameter of less than about 0.29 nm.

Further, in a suitable configuration according to the present invention, the framework structure may be a skeletal silicate of the class of Strunz 09.F, such as Cancrinite, May be a skeletal silicate such as leucite, such as Leucite, or a skeletal germanium salt, and particularly skeletal silicates that do not contain zeolite water containing additional anions (see, e. G., The ninth edition of Stratz & ).

Of suitable skeletal structures, especially skeletal silicates, are particularly suitable skeletal silicates with sodalite framework topography. Soda lime minerals are particularly preferred. The sodalite present in nature has a composition of Na ₈ [(Cl, OH) ₂ Al ₆ Si ₆ O ₂₄ ] (= 6Na [AlSiO ₄ ] .2Na (Cl, OH)). In this case, the framework structure is formed by the aluminum-silicate-anions present in the form of beta cages. Some of the chloride, hydroxide, and sodium ions are generally inserted into the beta cages. Of course, in further embodiments, suitable sodalite structures can replace NaCl and / or NaOH. Also, instead of NaCl and NaOH, sodalite frameworks in which a sodium polysulfide such as Na ₂ S _n , such as Na ₂ S ₆ , is inserted into the beta cages are also desirable. Soda lite belongs to the Strutz 09.FB.10 group (according to the 9th edition of the Strutz mineral taxonomy).

Also, in the case of skeletal silicates, up to 50% of the tetrahedral tetrahedral units may be replaced by tetrahedral structural units comprising trivalent center atoms, especially aluminum.

Especially preferred skeletal silicates are zeolites.

The microporous anionic inorganic framework structures comprising monovalent dopant cations or alkaline ions, particularly sodium ions, are preferably used for thin film solar cells in which the semiconductor light absorbing layer forms a kesterite or a brass light semiconductor light absorbing layer Is used. The above-described kestelite and chalcopyrite semiconductor light absorbing layers suitable for thin film solar cells and their manufacture are well known to those skilled in the art. In addition, in an embodiment of the thin film solar cell according to the present invention, the semiconductor light absorbing layer may be a quaternary IB-IIIA-VIA brass layer, particularly a Cu (In, Ga) Se ₂ layer, , Particularly a Cu (In, Ga) (Se _{1 -x} , S _x ) ₂ layer or a casterite layer, in particular a Cu ₂ ZnSn (Se _x , S _{1 -x} ) ₄ layer such as Cu ₂ ZnSnSe ₄ Cu ₂ ZnSnS ₄ layer, or may include these layers, and x has a value of 0 to 1.

In addition, the object of the present invention is also to provide a photoelectric thin film comprising microporous anionic inorganic framework structures, in particular skeletal silicates or skeletal germanate salts, in at least one of a back electrode layer, at least one contact layer, and / It is solved by solar cells. In this way, based on the inert nature of the framework structures used here, impurities from the thin film solar cell, such as Fe ^{3 +} and / or Ni ^{2 +,} are absorbed.

In this case, in a particularly suitable embodiment, alternatively or additionally, a microporous anionic inorganic framework structure comprising metal ions from the semiconductor photoabsorption layer in the micropores, such as Cu ⁺ , Ga ^{3 +} and / or In ^{3 +} May be present in the thin film solar cell.

It has proved to be very particularly preferred that the semiconductor light absorbing layer is doped with monovalent dopant cations originally derived from the skeleton structures, in particular alkali ions, in particular in the exchange with the metal ions of the semiconductor light absorbing layer, Are examples of thin film solar cells according to the present invention.

A preferred embodiment of the thin film solar cell according to the present invention comprises, in the stated order,

- at least one substrate layer, in particular in the form of a glass plate,

At least one first barrier layer, in particular nonconductive, depending on the case,

At least one rear electrode layer,

- optionally one or more second conductive barrier layers and one or more particularly ohmic contact layers,

At least one semiconductor light absorbing layer, in particular a brass or casterite semiconductor light absorbing layer, directly adjacent to the back electrode layer or the contact layer,

- optionally at least one first buffer layer,

- optionally at least one second buffer layer,

At least one front electrode layer.

The general and specific descriptions made above for the applications according to the invention apply in the same way to the thin film solar cells and thin film solar modules according to the invention.

The thin film solar cells according to the present invention comprise microporous anionic inorganic framework structures of the type, especially skeletal silicates, of the type comprising or consisting of especially tetrahedral structural units. Suitable skeletal silicates for use in the thin film solar cells according to the present invention include aluminosilicate silicate, titanium aluminosilicate silicate, boron skeletal silicate, gallo skeletal silicate, indium skeletal silicate, and ferro (III) skeletal silicate.

In this case, particularly suitable skeletal structures, in particular skeletal silicates, consist of so-called beta cages, in particular enriched beta cages, or comprise said beta cages.

Particularly suitable skeletal structures, especially skeletal silicates, for the thin film solar cells according to the invention are not hygroscopic.

In the thin film solar cell according to the present invention preferably in the skeleton structure having micropores, in particular a skeleton silicate are used, micropores are, the metal ion of the metal of the light absorbing layer, such as Cu ^+, Ga ^{3 +} and / or by in ^{3 +,} and / or a thin film of an impurity from the solar cell, for example, Fe ^{3 +} and / or Ni ^{2 +,} the first dopant cation present in the microporous, in particular porous, which allows the exchange of alkali ions And has an opening diameter.

The thin film solar cells according to the present invention are characterized by having skeleton structures in the semiconductor light absorbing layer, particularly those containing microparticles of sodium ions, potassium ions, lithium ions, rubidium ions and / or cesium ions, , Especially skeletal silicates. In this case, suitable framework structures, particularly skeletal silicates, include micropores having a porous opening diameter of less than about 0.29 nm in a particularly preferred embodiment. When using skeletons having a porous opening diameter of less than about 0.29 nm, they can be processed particularly efficiently, without interference of water molecules. The water molecules do not reach the micropores of the framework structures in the case of the diameter of the microporous opening, and they do not leak out from the micropores.

Certainly suitable for the thin film solar cells according to the invention are skeletal structures, especially skeletal silicates, including sodite skeletal topography, in particular sodalite itself.

Particularly suitable embodiments of the thin film solar cells according to the invention are also characterized in that up to 50% of quadrivalent tetrahedral units use skeletal silicates substituted with tetrahedral structural units comprising trivalent central atoms, especially aluminum Given.

According to the present invention, crystalline skeletal silicates, especially crystalline alkali silicates, are preferably used.

In a further configuration, in the case of the thin film solar cells according to the invention, the first buffer layer may comprise or substantially consist of CdS, or in particular Zn (S, O), Zn (S, And / or a CdS-free layer comprising or substantially consisting of In ₂ S ₃ , and / or wherein the second buffer layer comprises an intrinsic zinc oxide and / or a high resistance zinc oxide, As shown in FIG.

Also, the contact layer may comprise at least one metal layer and at least one metal chalcogenide layer, wherein the metal layer is adjacent to or in contact with the rear electrode, or adjacent to or in contact with the barrier layer, Thin film solar cells according to the present invention are also suitable, wherein the metal chalcogenide layer is adjacent to or in contact with the semiconductor light absorbing layer.

In this case, in particular, the metal layer and the metal chalcogenide layer may be based on the same metal, especially molybdenum and / or tungsten.

Particularly preferably, the contact layer also forms a metal chalcogenide layer.

In addition, the object of the invention is solved by a thin film solar module comprising solar cells according to the invention, in particular connected in series in monolithic integration manner, as described in the general case and the special case above.

The present invention also provides a method for manufacturing a photovoltaic thin film solar cell or a photovoltaic thin film solar module according to the present invention, and more particularly to a method for manufacturing a photovoltaic thin film solar cell or a photovoltaic thin film solar module, One or more of the back electrode layers, one or more contact layers, and / or one or more semiconductor light absorbing layers of one or more thin film solar cells that form a thin film solar module based on a glass substrate layer in the form of a glass plate, And / or incorporating and / or introducing microporous anionic inorganic skeletal structures, especially skeletal silicates or skeletal germanic acid salts, onto and /

In a particularly suitable configuration of the method,

- providing a particularly planar substrate, in particular in the form of a glass sheet or a glass sheet,

- optionally applying a first barrier layer which is non-conductive on the substrate,

- applying one or more back electrode layers onto the substrate or first barrier layer by physical and / or chemical vapor deposition from one or more first material sources;

- optionally, applying one or more second conductive barrier layers onto the one or more back electrode layers by physical and / or chemical vapor deposition from one or more second material sources

Applying one or more particularly ohmic contact layers on the second barrier layer by physical and / or chemical vapor deposition from one or more third material sources, or

Applying at least one first metal layer from the at least one fourth material source to the second barrier layer to form a contact layer together by physical and / or chemical vapor deposition;

Metal components of the semiconductor light absorbing layer of copper, indium and possibly gallium in the case of a brass optical semiconductor light absorbing layer, in particular on the back electrode layer or on the contact layer by physical and / or chemical vapor deposition from one or more fifth material sources, Depositing at least one second metal layer comprising metal components of a semiconductor light absorbing layer of copper, zinc and tin in the case of a kestellite semiconductor light absorbing layer;

- in particular by one or more wet deposition processes and / or by physical and / or chemical vapor deposition, from one or more sixth material sources, onto a substrate layer, and / or onto a back electrode layer, And / or on the second barrier layer, and / or optionally on the contact layer, and / or optionally on the first metal layer, and / or on the second metal layer, the microporous anionic inorganic framework structures, And / or optionally with one or more of the first and / or second barrier layers, and / or optionally with one or more of the backside electrode layers, and / Co-depositing the framework structures together with one or more first metal layers, and / or optionally with one or more first metal layers, and /

- at least 300 [deg.] C with at least sulfur and / or selenium compounds and / or gaseous element selenium and / or sulfur if the second metal layer is placed on the back electrode layer or, if appropriate, on the first metal layer Treating the second metal layer while forming a semiconductor light absorbing layer at an upper temperature, in particular in the range of 350 ° C to 600 ° C, preferably in the range of 520 ° C to 600 ° C,

- optionally, applying at least one first buffer layer on the semiconductor light absorbing layer;

- optionally, applying at least one second buffer layer on the first buffer layer or the semiconductor light absorbing layer,

- applying at least one transparent front electrode layer on the first or second buffer layer or the semiconductor light absorbing layer.

In a preferred manner, embodiments of the process according to the invention in which the microporous anionic inorganic skeletons, in particular skeletal silicates or skeletal germanates, contain monovalent dopant cations, especially alkali ions, in the micropores are particularly suitable.

The second tempering step referred to above can be used in a preferred configuration to form a semiconductor light absorbing layer and / or to form a back electrode layer comprising or consisting of metal selenides, as well as a metal ion In the micropores of the framework structure with impurities such as Cu ⁺ , Ga ^{3 +} and / or In ^{3 +} , and / or impurities in the thin film solar cell, such as Fe ^{3 +} ions and / or Ni ^{2 +} Lt; Desc / Clms Page number 2 > exchange of the dopant cations or alkaline ions, especially sodium ions, from the resulting solution. The exchange of these ions does not destroy the anion lattice of the framework structure in a desirable way, and the crystal structure of the skeletal structure does not change as a result.

In a particularly suitable configuration, the physical vapor deposition can each be performed by a physical vapor deposition (PVD) coating, a deposition using an electron beam evaporator, a deposition using a resistive evaporator, an inductive deposition, an ARC deposition and / or a cathode sputtering (sputter coating) , In particular DC or RF magnetron sputtering, and chemical vapor deposition includes chemical vapor deposition (CVD), low pressure CVD and / or atmospheric pressure CVD.

For the deposition of microporous anionic inorganic framework structures, especially skeletal silicates or skeletal germanate salts, the use of one or more wet deposition processes is preferred. In this case, for example, brush coating, roller coating, sputtering or spray coating, injection, application with a blade, and / or inkjet printing or aerosol printing may be used. Thus, for the deposition of microporous anionic inorganic framework structures, in particular spray methods known to those skilled in the art can be used, or an emulsion or an aqueous system, such as a deposition into an aqueous solution, can be used.

Also, the first material source and the sixth material source form a first mixed target, and / or the second material source and the sixth material source form a second mixed target, and / or the third material source and / 6 material source forms a third mixed target, and / or the fourth material source and the sixth material source form a fourth mixed target, and / or the fifth material source and the sixth material source form a fifth mixed target Are also preferred.

Also from the fifth, sixth and first material sources or from the fifth, sixth and third material sources or from the fifth, sixth and fourth material sources, or from the fifth mixed target and the first material source Or from the fifth mixed target and the third material source, or from the fifth mixed target and the fourth material source, sequentially, or substantially concurrently.

Also, in one configuration, co-deposition may be performed sequentially, or substantially concurrently, from the fifth mixed target and the fifth material source.

According to a further suitable configuration of the method according to the invention, it is possible to obtain from the first, second, third and / or fourth mixed target, in particular from the first, third or fourth mixed target and the fifth material source, , Or substantially simultaneously, is performed.

Alternatively, co-deposition may be performed sequentially, or substantially concurrently, from the fifth mixed target and the first, second, third and / or fourth mixed targets, particularly from the first or third or fourth mixed target It is possible.

According to a further construction of the method according to the invention, it is possible to obtain from a first, second or third mixed target, in particular a first or a third mixed target, and a first, second, third or fourth material source, Or from a third or fourth material source, sequentially, or substantially simultaneously, is carried out.

Cu-layers, In-layers and Ga-layers for forming a backside electrode layer, an optional conductive barrier layer and in particular a brass-optical semiconductor light absorbing layer, or Cu layers for forming a kestellite semiconductor light absorbing layer, Zn- , And a first metal layer or contact layer of metals in the semiconductor light absorbing layer of Sn-layers, and microporous anionic inorganic framework structures comprising monovalent dopant cations, particularly alkali ions, preferably sodium ions, in the micropores , In particular skeletal silicates or skeletal germanium salts, is preferably carried out in a single vacuum coating facility, preferably in a continuous sputtering process.

The present invention is based on the use of semiconductor light absorbing layers of thin film solar cells, in particular glass substrates, for example, semiconductor light absorbing layers which are present in the form of, for example, glass plates or which contain glass plates can efficiently and reliably Is doped with dopant cations or alkaline ions, especially sodium ions. Therefore, the amounts of dopant cations or alkaline ions, especially sodium ions, introduced into the semiconductor light absorbing layer can be precisely quantified, and dopant cations or alkaline ions that act electrically compared to the actually introduced dopant cations or alkaline ions, High utilization of sodium ions is achieved. Such doped thin film solar cells according to the present invention allow to achieve high efficiency in a repeatable manner. Thin film solar cells and modules according to the present invention do not involve the risk of generating electrical defects, and thus do not involve increased hygroscopicity, despite doping with monovalent dopant cations to alkaline ions. In principle, there is no longer a need to introduce foreign substances into a thin film solar cell. In addition, doping according to the present invention using monovalent dopant cations or alkaline ions, especially sodium ions, is also handled without the use of completely sensitive and / or toxic materials, and water or other oxygen- It does not flow into the light absorbing layer. Thus, for example, particularly efficient hygroscopic degradation products are prevented. In addition, particularly preferably, uniform distribution of monovalent dopant cations to alkaline ions, especially sodium ions, is achieved over the entire width of the semiconductor light absorbing layer. Therefore, the lateral non-uniformity can be completely or almost completely excluded. In addition, for the first time, efficient exchange of monovalent dopant cations to alkali ions, especially sodium ions, with cations of the semiconductor light absorbing layer, such as copper ions, can be ensured.

Claims (50)

Microporous anionic inorganic framework structures, especially skeletal silicates, in thin film solar cells or thin film solar modules based on a glass substrate layer, in particular for absorbing impurities from thin film solar cells and / or thin film solar modules, Use of skeletal Germanium salts. The method of claim 1, wherein the microporous anionic inorganic framework structures, particularly skeletal silicates or skeletal germanates, comprise one or more back electrode layers, one or more contact layers, and / or one or more semiconductor light absorbing layers of a thin film solar cell or thin film solar module Lt; RTI ID = 0.0 > a < / RTI > anionic inorganic skeleton structure. The method according to claim 2, characterized in that said thin film solar cell or said thin film solar module, in particular at least one semiconductor light absorbing layer of said thin film solar cell and / or said thin film solar module, comprises monovalent dopant cations, The use of microporous anionic inorganic framework structures. In particular, for the production of the semiconductor light absorbing layer in which the semiconductor light absorbing layer of the thin film solar cell and / or the thin film solar module based on the glass substrate layer and corresponding monovalent dopant cations are provided, the monovalent dopant cations Especially microporous anionic inorganic skeletons, especially skeletal silicates or skeletal germanates, containing alkali ions. 5. The method of claim 4, further comprising the step of removing from the monovalent dopant cations, especially alkali ions, one or more of the thin film solar cells and / or one or more of the back electrode layers, the one or more contact layers, and / Microporous anionic inorganic framework structures, particularly skeletal silicates or skeletal germanates, which are liberated into the semiconductor light absorbing layer can be applied to the thin film solar cell and / or one or more of the back electrode layer, the at least one contact layer, and / The use of the microporous anion inorganic framework structure is characterized by being present in the semiconductor light absorbing layer. Monovalent dopant cations, microporous anionic inorganic framework structures comprising said monovalent dopant cations, especially alkali ions, in the micropores for doping a semiconductor light absorbing layer of thin film solar cells and / or thin film solar modules, Especially skeletal silicates or skeletal germanium salts. 7. The microporous anion inorganic framework structure according to any one of claims 1 to 6, characterized in that the microporous anionic inorganic framework structures, in particular skeletal silicates, comprise or are formed from tetrahedral structural units. Usage. 8. Use of a microporous anionic inorganic framework according to any one of claims 1 to 7, characterized in that the framework structure, in particular skeletal silicates, is not hygroscopic. Article according to any one of the preceding claims, wherein the framework structure, in particular backbone microporous of silicates or framework germanium acid salts include, the metal ion of the metal of the light absorbing layer, such as Cu ^+, Ga ^{3 +} and / or And has a pore opening diameter enabling the exchange of univalent dopant cations in the micropores, particularly alkali ions, with In ^< ^{3 + &} gt ;. 10. The composition of any one of claims 1 to 9, wherein the skeletal silicate is an aluminosilicate silicate, a titanium aluminosilicate silicate, a boron skeletal silicate, a gallo skeletal silicate, an indium skeletal silicate, or a ferro (III) Use of a microporous anionic inorganic skeletal structure. 11. The microporous anionic inorganic skeleton structure according to any one of claims 1 to 10, characterized in that the skeletal structure, in particular the skeletal silicate, comprises or consists of beta cages, in particular concentrated beta cages. Use of. 12. A process according to any one of claims 1 to 11, wherein the skeleton structure, in particular the skeleton silicate, contains sodium ions, potassium ions, lithium ions, rubidium ions and / or cesium ions, Wherein the microporous anionic inorganic skeleton structure comprises sodium ions. 13. Use of a microporous anionic inorganic framework according to any one of the preceding claims, characterized in that the framework structure, in particular the skeletal silicate, comprises micropores having a pore opening diameter of less than about 0.29 nm. 14. Use of a microporous anionic inorganic framework according to any one of claims 1 to 13, characterized in that the framework structure, in particular the skeletal silicate, has a sodite skeletal topography. 15. A method according to any one of claims 1 to 14, wherein up to 50% of the tetrahedral tetrahedral units of the skeletal silicate are replaced by tetrahedral structural units comprising trivalent central atoms, especially aluminum Use of microporous anionic inorganic frameworks. 16. A process according to any one of claims 1 to 15, wherein said framework is selected from the group consisting of skeletal silicates or skeletal germanium salts of the class of Sturz's 09.F or 09.G, in particular skeletons not containing zeolite water containing further anions Lt; RTI ID = 0.0 > a < / RTI > silicate. 17. Use of a microporous anionic inorganic framework according to any one of the preceding claims, wherein the skeletal silicate is zeolite. The use of the microporous anion inorganic framework structure according to any one of claims 1 to 17, wherein the semiconductor light absorbing layer is a kestellite or a brass optical semiconductor light absorbing layer. In particular, a photovoltaic thin film solar cell comprising microporous anionic inorganic framework structures, particularly skeletal silicates or skeletal germanate salts, in at least one of a backside electrode layer, at least one contact layer, and / or one or more semiconductor light absorbing layers. 20. The method of claim 19, wherein the microporous anionic inorganic framework structures comprise metal ions such as Cu ⁺ , Ga ^{3 +} and / or In ^{3 +} , and / or impurities from a thin film solar cell, For example, Fe ^{3 +} and / or Ni ^{2 +} . 21. The semiconductor light absorbing layer according to claim 19 or 20, wherein the semiconductor light absorbing layer is doped with monovalent dopant cations originally derived from the skeleton structures, in particular, alkali ions, in particular by exchange with metal ions of the semiconductor light absorbing layer A photovoltaic thin film solar cell characterized by. 22. The method according to any one of claims 19 to 21,
- at least one substrate layer, in particular in the form of a glass plate,
At least one first barrier layer, in particular nonconductive, depending on the case,
At least one rear electrode layer,
- optionally one or more second conductive barrier layers and one or more particularly ohmic contact layers,
- at least one semiconductor light absorbing layer, in particular a brass or casterite semiconductor light absorbing layer, directly adjacent to said back electrode layer or said contact layer,
- optionally at least one first buffer layer,
- optionally at least one second buffer layer,
A photovoltaic thin film solar cell comprising at least one front electrode layer. 24. The photovoltaic thin-film solar cell according to any one of claims 19 to 22, wherein the microporous anionic inorganic framework structures, particularly skeletal silicates, comprise or are formed from tetrahedral structural units. 24. The photovoltaic thin film solar cell according to any one of claims 19 to 23, wherein the skeletal structure, particularly skeletal silicate, is not hygroscopic. A method according to any one of claim 19 through claim 24, wherein the framework structure, in particular a microporous of the skeleton silicate are metal ion of the metal of the semiconductor light absorption layer, such as Cu ^+, Ga ^{3 +} and / or In ^{3 +} , And / or a porous opening diameter allowing the exchange of dopant cations, particularly alkali ions, in the micropores with impurities produced in the thin film solar cell, such as Fe ^{3 +} and / or Ni ^{2 +} A photovoltaic thin film solar cell. 26. The method according to any one of claims 19 to 25, wherein the skeletal silicate is an aluminosilicate silicate, a titanium aluminate skeletal silicate, a boron skeletal silicate, a gallo skeletal silicate, an indium skeletal silicate, or a ferro (III) A photovoltaic thin film solar cell characterized by. 27. The photovoltaic thin film solar cell according to any one of claims 19 to 26, wherein the skeletal structure, in particular the skeletal silicate, comprises or consists of beta cages, especially concentrated beta cages. 28. A process according to any one of claims 19 to 27, wherein said skeleton structure, in particular skeleton silicate, contains sodium ions, potassium ions, lithium ions, rubidium ions and / or cesium ions, Wherein the photovoltaic cell comprises sodium ions. 29. The photovoltaic thin film solar cell according to any one of claims 19 to 28, wherein the skeletal structure, in particular the skeletal silicate, comprises micropores having a pore opening diameter of less than about 0.29 nm. 30. The photovoltaic thin film solar cell according to any one of claims 19 to 29, wherein the skeletal structure, particularly the skeletal silicate, has sodalite skeletal topography. 31. The method according to any one of claims 19 to 30, wherein up to 50% of the tetrahedral tetrahedral units of the skeletal silicate are replaced by tetrahedral units comprising a trivalent central atom, especially aluminum Photovoltaic thin film solar cell. 32. A method according to any one of claims 19 to 31, wherein said framework is selected from the group consisting of skeletal silicates or skeletal germanium salts of the class of Stratz 09.F or 09.G, in particular skeletons which do not contain zeolite water containing further anions Lt; RTI ID = 0.0 > photovoltaic < / RTI > thin film solar cell. 32. The photovoltaic thin film solar cell according to any one of claims 19 to 32, wherein the skeletal silicate is zeolite. 34. The method of any one of claims 22 to 33, wherein the first buffer layer comprises or substantially consists of CdS, or in particular Zn (S, O), Zn (S, including / or in ₂ S _3, or virtually can not CdS- layer composed of these, and / or the second buffer layer that includes the intrinsic zinc oxide and / or zinc oxide, or a high-resistance or substantially formed from these Wherein the photovoltaic cell is a photovoltaic cell. 34. The semiconductor light-absorbing layer according to any one of claims 19 to 34, wherein the semiconductor light absorbing layer is a quaternary IB-IIIA-VIA brass layer, particularly a Cu (In, Ga) Se ₂ layer, In particular, Cu (In, Ga) (Se 1-x, S x) 2 layer, or a light cake stacking layer, in particular _{Cu 2 ZnSn (Se x, S} 1 -x) 4 layer, such as Cu ₂ ZnSnSe layer _4, or Cu ₂ ZnSnS ₄ layer, or a layer containing these layers, wherein x has a value of 0 to 1. 37. A method according to any one of claims 19 to 35, wherein the contact layer comprises at least one metal layer and at least one metal chalcogenide layer, the metal layer being adjacent to or bordered by the back electrode Or the barrier layer is in contact with a boundary of the barrier layer, and the metal chalcogenide layer is adjacent to the semiconductor light absorbing layer or in contact with the boundary of the semiconductor light absorbing layer. 37. The photovoltaic thin film solar cell of claim 36, wherein the metal layer and the metal chalcogenide layer are based on the same metal, especially molybdenum and / or tungsten. 37. The photovoltaic thin film solar cell according to any one of claims 19 to 37, wherein the contact layer is or comprises a metal chalcogenide layer. 38. A photovoltaic solar module according to any one of claims 19 to 38, comprising solar cells connected in series, in particular in monolithic integration. 39. A method for manufacturing a photovoltaic thin film solar cell according to any one of claims 1 to 38, or a photovoltaic thin film solar module according to claim 39,
One or more thin film solar cells based on a glass substrate layer, or one or more back electrode layers of one or more thin film solar cells that form a thin film solar module based on the glass substrate layer in particular, one or more contact layers, and / Wherein the microporous anionic inorganic framework structures, especially skeletal silicates or skeletal germanates, are applied or introduced onto and / or within the light absorbing layer. 41. The method of claim 40,
- providing a particularly planar substrate, in particular in the form of a glass sheet or a glass sheet,
- optionally applying a first barrier layer which is non-conductive on the substrate,
- applying one or more back electrode layers onto the substrate or the first barrier layer by physical and / or chemical vapor deposition from one or more first material sources;
- optionally, applying one or more second conductive barrier layers onto the one or more back electrode layers by physical and / or chemical vapor deposition from one or more second material sources
Applying one or more particularly ohmic contact layers on the second barrier layer by physical and / or chemical vapor deposition from one or more third material sources, or
Applying at least one first metal layer from the at least one fourth material source to the second barrier layer to form the contact layer together by physical and / or chemical vapor deposition;
- metal components of the semiconductor light absorbing layer of copper, indium and occasionally gallium in the case of a brass optical semiconductor light absorbing layer, on the said back electrode layer or said contact layer, by physical and / or chemical vapor deposition from one or more fifth material sources Depositing at least one second metal layer comprising metal components of a semiconductor light absorbing layer of copper, zinc and tin in the case of a kestellite light absorbing layer;
In particular by one or more wet deposition processes, and / or by physical and / or chemical vapor deposition, from one or more sixth material sources, onto the substrate layer, and / or onto the rear electrode layer, On the first and / or second barrier layer, and / or as the case may be, on the contact layer, and / or optionally on the first metal layer and / or on the second metal layer, Anionic inorganic skeletal structures, in particular skeletal silicates or skeletal germanium salts, and / or with the one or more rear electrode layers and / or optionally with the one or more first and / or second barrier layers, And / or optionally with the at least one contact layer, and / or optionally with the at least one first metal layer, and / or with the at least one second metal layer, Depositing,
And / or as at least sulfur and / or selenium compounds if the second metal layer is seated on the back electrode layer or, if appropriate, Treating the second metal layer while forming the semiconductor light absorbing layer at a temperature higher than 300 캜, particularly 350 캜 to 600 캜, preferably 520 캜 to 600 캜,
- optionally, applying at least one first buffer layer on the semiconductor light absorbing layer;
- optionally, applying one or more second buffer layers on the first buffer layer or the semiconductor photoabsorption layer;
- applying at least one transparent front electrode layer on the first or second buffer layer or the semiconductor light absorbing layer
A method of manufacturing a photovoltaic thin film solar cell or a photovoltaic thin film solar module. 42. A process according to claim 40 or claim 41, wherein said microporous anionic inorganic framework structures, in particular skeletal silicates or skeletal germanates, contain monovalent dopant cations in said micropores, in particular alkali ions. A method of manufacturing a thin film solar cell or a photovoltaic thin film solar module. 43. A method according to any one of claims 40 to 42, wherein the physical vapor deposition is performed by a physical vapor deposition (PVD) coating, preferably with a high vacuum, a deposition using an electron beam evaporator, a deposition using a resistive evaporator, Wherein the chemical vapor deposition includes chemical vapor deposition (CVD), low pressure CVD, and / or atmospheric pressure CVD, and / or a cathode sputtering (sputter coating), particularly DC or RF magnetron sputtering. A method of manufacturing a photovoltaic thin film solar module. 44. The method according to any one of claims 40 to 43,
Wherein the first material source and the sixth material source form a first mixed target and / or the second material source and the sixth material source form a second mixed target, and / or the third material And / or said fourth material source and said sixth material source form a fourth mixed target, and / or said fifth material source and said sixth material source form a third mixed target, and / or said fourth material source and said sixth material source form a fourth mixed target, 6 material source forms a fifth mixed target. ≪ RTI ID = 0.0 > 11. < / RTI > 45. A method according to any one of claims 40 to 44, further comprising the steps of: from the fifth, sixth and first material sources, or from the fifth, sixth and third material sources, 4 material source, or from said fifth mixed target and said first material source, or from said fifth mixed target and said third material source, or from said fifth mixed target and said fourth material source, sequentially Wherein the co-deposition is carried out substantially simultaneously. ≪ RTI ID = 0.0 > 15. < / RTI > The photovoltaic thin film solar cell or photoelectric thin film according to any one of claims 40 to 45, characterized in that coevaporation is performed sequentially, or substantially simultaneously, from the fifth mixed target and the fifth material source A method of manufacturing a solar module. 47. A method according to any one of claims 40 to 46, wherein said first, second, third and / or fourth mixed target, in particular said first, third or fourth mixed target and said fifth material source Wherein the co-deposition is performed sequentially, or substantially simultaneously, from at least one of the plurality of photovoltaic solar cells or the photovoltaic solar module. 47. A method according to any one of claims 40 to 47, wherein said fifth mixed target and said first, second, third and / or fourth mixed target, in particular said first, Wherein the co-deposition is performed sequentially, or substantially simultaneously, from at least one of the plurality of photovoltaic solar cells or the photovoltaic solar module. 49. A method according to any one of claims 40 to 48, wherein the first, second, or third mixed target, particularly the first or third mixed target, and the first, second, Characterized in that co-deposition is performed sequentially, or substantially concurrently, from the four-material source, especially the first, third or fourth material source. 50. The method of any one of claims 40-49, wherein the back electrode layer, the conductive barrier layer as the case may be, and in particular the Cu-layers, In-layers and Ga-layers for forming a brass- A first metal layer or contact layer of metals in the semiconductor light absorbing layer of Cu-layers, Zn-layers and Sn-layers for forming a stellite light absorbing layer, and alkali ions, particularly sodium ions, in the micropores Characterized in that the application of the microporous anionic inorganic framework structures, in particular the skeletal silicates or the skeletal germanates, is carried out in a single vacuum coating facility, preferably in a continuous sputtering process. ≪ / RTI >