1. Field of the Invention
This invention generally relates to solar cells and, more particularly, to a mesoporous-structure solar cell using a siloxane barrier.
2. Description of the Related Art
As evolved from dye-sensitized solar cells (DSSCs or DSCs), perovskite-sensitized solar-cells have recently attracted a great deal attention with a record high efficiency breakthrough (>17%) based upon low cost organometal trihalide perovskite absorbers. It has been suggested that with optimization of the cell structure, light absorber, and hole conducting material, this technology could advance to an efficiency that surpasses that of copper indium gallium (di)selenide (CIGS) (20%) and approaches crystalline silicon (25%). Conventional perovskite based solar cells use two common types of architecture: flat and mesoscopic. With the flat architecture, one absorber layer is deposited directly on a flat (planar) titanium oxide (TiO2) surface forming a thin film, in a fashion similar to thin film solar cells. The second approach adopts a configuration similar to solid dye-sensitized solar cells.
The mesoporous TiO2 electrode 106 has long been the most commonly used electron transporter material since the advent of liquid DSC. This porous TiO2 structure provides sufficient internal surface area to which dye molecules can attach and, therefore, maximizes light harvesting efficiency. The electron transfer from selected dyes to the porous TiO2 electrode is not only a favored process but is also much faster than other recombination processes, making porous TiO2 an indispensable photo anode for DSC. In addition, mesoporous TiO2 participates in light scattering, thus improving the photocurrent.
Despite the remarkable photovoltaic performances that have been demonstrated for the perovskite cells, a PCE as high as 15%, a number of issues remained. One of the challenges is related to the overall devices stability, especially the decomposition of the perovskite material in the presence of moisture and light, or the combination these effects. In addition, the crystallization of the perovskite material on the TiO2 surface is random, thus leading to polycrystallinity and potential problems with grain boundaries. Moisture can be effectively blocked through appropriate packaging of the solar cell. However, the problem of perovskite decomposition at the TiO2/perovskite interface remains (Nature Comm., 2013, 4, 2885). This is because the perovskite-to-TiO2 contact is different from that of dye-to-TiO2, although the perovskite cell is a natural extension of ssDSC and the electron injection process remains preferred. In recent work (Science, 2012, 338 (6107), 643), a mesoporous network of the aluminum oxide was used as a scaffold for the perovskite structure. The cell performed better than that with the TiO2 mesoporous network. The open circuit voltage was noticeably higher for Al2O3 than TiO2, suggesting that there was less charge recombination in Al2O3. In this case, the transport of the negative charges occurs through the network of the perovskite material, as injection of electron into Al2O3 is energetically unfavorable. This result implies that charge injection from perovskite to TiO2 is energetically favorable, but the imperfections at the interface act as recombination centers and further affect the device stability. Therefore, a proper interface between the perovskite absorber layer and TiO2 would not only improve cell performance by eliminating those recombination centers but also help to achieve long term stability in such devices.
It would be advantageous if the perovskite interface in a mesoporous structure solar cell could be improved to increase stability and reduce recombination centers.
Disclosed herein is a solar cell where the mesoporous surfaces have been effectively passivated. The passivating molecules not only serve as anchors for perovskite to link onto, but also prevent its decomposition from occurring upon light irradiation. The requirements for selecting the effective anchoring agent are two-fold. First, the passivating molecules should have an affinity towards the perovskite structure or participate in the perovskite structure formation. The amine or ammonium group can facilitate the proper formation of the perovskite layer. Second, the other end of the passivating molecule should have an affinity towards the mesoporous metal oxide surface, so that it is capable of providing good passivation for all the trap sites on the surface of the metal oxide. Aminosilanes or aminosiloxanes perform such a function. These two active ends can be connected via an organic hydrocarbon chain, and the length of the organic chain also controls the electron transfer/injection efficiency from the perovskite into the mesoporous metal oxide.
Accordingly, a method is provided for forming a mesoporous-structured solar cell with a silane or siloxane barrier. The method forms a transparent conductive electrode overlying a transparent substrate. A non-mesoporous layer of a first metal oxide overlies the transparent conductive electrode, with a mesoporous layer of a second metal oxide overlying the non-mesoporous layer of first metal oxide. An aminoalkoxysilane layer overlies the mesoporous layer of second metal oxide. Over the aminoalkoxysilane layer is deposited a semiconductor absorber layer prepared from organic and inorganic precursors. Using the aminoalkoxysilane, the mesoporous layer of second metal oxide is linked to the semiconductor absorber layer. A hole-transport material (HTM) layer is formed overlying the semiconductor absorber layer, and a metal electrode overlies the HTM layer.
More explicitly, depositing the aminoalkoxysilane layer includes the aminoalkoxysilane having a structure comprising A-L-B;
where B is a derivative of amino or ammonium;
where “A” is represented with a formula Si(OR)3,
where L is a derivative of linear alkanes, branched alkanes, cycloalkanes, (poly)cycloalkanes, cis- and trans-linear alkenes, cis- and trans-branched alkenes, linear alkynes, branched alkynes, (poly)alkynes, aromatic hydrocarbons, (poly)aromatic hydrocarbons, heteroarenes, (poly)heteroarenes, thiophenes, (poly)thiophenes, (poly)anilines, or combination of above-recited elements.
Some examples of the first and second metal oxides, which may be the same or different material, include titanium oxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), barium titanate (BaTiO3), strontium titanate (SrTiO3), zinc titanate (ZnTiO3), and copper titanate (CuTiO3). The HTM layer may be an organic HTM material such as spiro-OMeTAD.
The semiconductor absorber layer has the general formula of FEXZY3-Z;
where F is an organic monocation;
where E is a transition metal dication;
where X and Y are inorganic monoanions; and,
where Z is in a range of 0 to 1.5.
Additional details of the above-described method, a mesoporous-structured solar cell with a silane or siloxane barrier, and a related composite material are presented below.
Generally, the first metal oxide 306 and second metal oxide 308 are both n-type metal oxides. More explicitly, the first metal oxide 306 and second metal oxide 308 are independently selected, meaning they may be the same or a different material, examples of which include titanium oxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), barium titanate (BaTiO3), strontium titanate (SrTiO3), zinc titanate (ZnTiO3), and copper titanate (CuTiO3). This is not an exhaustive list of possible metal oxides.
A semiconductor absorber layer 310 overlies the mesoporous layer of second metal oxide 308, comprising organic and inorganic components. An aminoalkoxysilane linker 312 links the semiconductor absorber layer 310 to the mesoporous layer of second metal oxide 308. A hole-transport material (HTM) layer 314 overlies the semiconductor absorber layer 310, and a metal electrode 316 overlies the HTM layer 314. Typically, the HTM layer 314 is an organic HTM material such as spiro-OMeTAD. However, the solar cell is not limited to any particular HTM material. The metal electrode 316 may be a highly conductive metal such as silver, aluminum, copper, molybdenum, nickel, gold, or platinum. Note: the drawing is not to scale.
The aminoalkoxysilane linker 312 has a structure comprising (—O)x—Si(OR)3-x-L-NR′3;
L is typically a derivative of linear alkanes, branched alkanes, cycloalkanes, (poly)cycloalkanes, cis- and trans-linear alkenes, cis- and trans-branched alkenes, linear alkynes, branched alkynes, (poly)alkynes, aromatic hydrocarbons, (poly)aromatic hydrocarbons, heteroarenes, (poly)heteroarenes, thiophenes, (poly)thiophenes, (poly)anilines, or combination of above-recited elements, and X is in the range of 1 to 3. In form of a linker, the aminoalkoxysilane is typically ammonium, but prior to linking it may have been either amino or ammonium. Upon attachment to the metal oxide surface and hydrolysis, the “OR” moieties are completely or partially lost. With TiO2 for example, the final linking would be Ti—O—Si. The other oxygen may participate in cross-linking, forming a secondary siloxane Si—O—Si structure. A siloxane is a functional group in organosilicon chemistry with the Si—O—Si linkage. The parent siloxanes include the oligomeric and polymeric hydrides with the formulae H(OSiH2)nOH and (OSiH2)n. Siloxanes also include branched compounds, the defining feature being that each pair of silicon centers is separated by one oxygen atom.
The semiconductor absorber layer 310 has the general formula of FEXZY3-Z;
where X and Y are inorganic monoanions; and,
where Z is in a range of 0 to 1.5.
The organic monocation F may be a substituted ammonium cation with the general formula of D1D2D3D4N;
where D may be hydrogen, or compounds derived from linear alkanes, branched alkanes, cycloalkanes, (poly)cycloalkanes, cis- and trans-linear alkenes, cis- and trans-branched alkenes, linear alkynes, branched alkynes, (poly)alkynes, aromatic hydrocarbons, (poly)aromatic hydrocarbons, heteroarenes, (poly)heteroarenes, thiophenes, (poly)thiophenes, (poly)anilines, or combination of above-recited elements;
where dication E may be Pb2+, Sn2+, Cu2+, Ge2+, Zn2+, Ni2+, Fe2+, Mn2+, Eu2+, or Co2+; and,
where the monoanions X and Y are independently selected from a group consisting of cyanides, thiocyanides, and halogenides including F—, Cl—, Br—, and I—. For example, the semiconductor absorber layer 310 may be CH3NH3Pbl3-XClX.
In one aspect, the combination of the second metal oxide layer 308, semiconductor absorber layer 310, and aminoalkoxysilane linker 312 may be considered to be composite material 318.
The general structure of such passivating-linker can have structures like: A-L-B, where “A” and B represent the functional aforementioned ends, and L represents the bridging group between the two functional ends. In particular, the group B may represent an amino or ammonium group; while group A can have a general formula such as Si(OR)3, in which the R group can be alkyl, unsaturated, and substituted or unsubstituted hydrocarbon (or modified with heteroatoms) moiety. The part L can be comprised of saturated, unsaturated or aromatic hydrocarbon molecules. Their length dictates the efficiency of the electron injection from semiconductor absorber to mesoporous metal oxide (e.g., perovskite to TiO2).
The coating of such a passivating material over mesoporous TiO2 nanoparticle network can be carried out by dipping the TiO2 substrate into diluted solution of siloxane followed by the exposure to air with optional heat treatment. This dip treatment only adds one extra step in the standard process flow of fabricating perovskite cells. Other solution-based methods could also be applied for the treatment of a metal oxide surface with the linker solution.
The approach illustrated in
Step 602 forms a transparent substrate, and Step 604 forms a transparent conductive electrode overlying the transparent substrate, which may be FTO, ITO, or IGZO, to name a few examples. Step 606 forms a non-mesoporous layer of a first metal oxide overlying the transparent conductive electrode. Step 608 forms a mesoporous layer of a second metal oxide overlying the non-mesoporous layer of first metal oxide. Step 610 deposits an aminoalkoxysilane layer overlying the mesoporous layer of second metal oxide. Step 612 deposits a semiconductor absorber layer, comprising organic and inorganic components, overlying the aminoalkoxysilane layer. Using the aminoalkoxysilane, Step 614 links the mesoporous layer of second metal oxide to the semiconductor absorber layer. Step 616 forms a HTM layer overlying the semiconductor absorber layer. Step 618 forms a metal electrode overlying the HTM layer. Generally, the method illustrated in
Depositing the aminoalkoxysilane layer in Step 610 includes the aminoalkoxysilane linker having a structure comprising A-L-B;
where B is a derivative of amino or ammonium;
where “A” is represented with a formula Si(OR)3,
where L is a derivative of linear alkanes, branched alkanes, cycloalkanes, (poly)cycloalkanes, cis- and trans-linear alkenes, cis- and trans-branched alkenes, linear alkynes, branched alkynes, (poly)alkynes, aromatic hydrocarbons, (poly)aromatic hydrocarbons, heteroarenes, (poly)heteroarenes, thiophenes, (poly)thiophenes, (poly)anilines, or a combination of above-recited elements. Upon attachment to the metal oxide surface and hydrolysis, the “OR” part is partially or completely lost. With, for example TiO2, the final linking would be Ti—O—Si.
Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as chloramine (NClH2). Ammonia is a compound of nitrogen and hydrogen with the formula NH3. The ammonium cation is a positively charged polyatomic ion with the chemical formula NH4+. It is formed by the protonation of ammonia (NH3). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary ammonium cations (NR4+), where one or more hydrogen atoms are replaced by organic radical groups (indicated by R).
The first and second metal oxides are independently selected from a group including titanium oxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), niobium oxide (Nb2O), tantalum oxide (Ta2Or), barium titanate (BaTiO3), strontium titanate (SrTiO3), zinc titanate (ZnTiO3), and copper titanate (CuTiO3). Forming the HTM layer in Step 616 includes forming an organic HTM material layer, such as spiro-OMeTAD.
Forming the semiconductor absorber layer in Step 612 includes forming a semiconductor absorber having a general formula of FEXZY3-Z;
where F is an organic monocation;
where E is a transition metal dication;
where X and Y are inorganic monoanions; and,
where Z is in a range of 0 to 1.5.
A mesoporous-structured solar call using an aminoalkoxysilane barrier and associated fabrication processes have been provided. Examples of particular materials and process steps have been presented to illustrate the invention. However, the invention is not limited to merely these examples. Other variations and embodiments of the invention will occur to those skilled in the art.
This application is a Continuation-in-part of a patent application entitled, SURFACE-PASSIVATED MESOPOROUS STRUCTURE SOLAR CELL, invented by Changqing Zhan et al., U.S. Ser. No. 14/320,488, filed Jun. 30, 2014, attorney docket No. SLA3383, which is incorporated herein by reference.
Number | Date | Country | |
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Parent | 14320488 | Jun 2014 | US |
Child | 14320702 | US |