Patent Application
20200294728
Perovskite materials, for example organic-inorganic halide perovskites, have drawn tremendous attention in recent years as promising candidates for the next generation of low-cost photovoltaics (PV). The power conversion efficiency (PCE) of perovskite solar cells (PSCs) has rapidly surged from <4% to 22.1% (certified), rivaling conventional thin film PV materials, such as CdTe and CIGS. Perovskites' high performance may originate from many of these materials' excellent optoelectronic properties, such as high absorption coefficient, low defect density and defect tolerance, long carrier lifetime, and advantageous diffusion length. More importantly, high performance PSCs can be fabricated through low cost solution processes. Indeed, PSCs are the first solution-processed solar cells that exceed the 20% efficiency benchmark. With continuous improvements in performance, stability and scaling-up of PSCs, their potential to revolutionize the PV industry is becoming more realistic than ever.
Despite this progress in cell efficiency, most researches have focused on lab-scale, e.g. small-area devices (<1 cm2), fabricated by spin coating. Thus, there remains significant need for the development of practical manufacturing methods for the full-scale production of large-area solar modules that integrate multiple sub-cells. There exists a gap between the lab-scale small-area devices and the large-area solar modules, as the spin coating process is not designed for uniform coating over large size substrates. Developing scalable deposition processes for scaling up the PSCs are essential for their practical applications and commercial adaption.
An aspect of the present disclosure is a perovskite-containing solar cell module that includes a glass substrate; a first cell; and a second cell, where each cell includes, in order, a first contact layer that includes fluorine-doped tin oxide, positioned on the substrate, and having an outside surface and a first thickness; an electron transfer layer that includes TiO2 and having a second thickness between 1 nm and 10 μm; an active layer that includes the perovskite and having a third thickness; a hole transfer layer that includes spiro-OMeTAD and having a fourth thickness; and a second contact layer that includes copper and having a fifth thickness. In addition, the first cell and the second cell are electrically connected by a first gap filled with the copper, and the first gap passes through the third thickness, the fourth thickness, and substantially through the second thickness to terminate at the outside surface.
An aspect of the present disclosure is a perovskite-containing solar cell module that includes a substrate having a first surface; a first cell; and a second cell, where each cell includes, in order, a first contact layer that includes a first material, positioned on the substrate, and having a second surface and a first thickness; an electron transfer layer (ETL) that includes a second material and having a second thickness; an active layer that includes the perovskite and having a third thickness; a hole transfer layer (HTL) that includes a third material and having a fourth thickness; and a second contact layer that includes a fourth material and having a fifth thickness. In addition, the first cell and the second cell are electrically connected by a first gap filled with the fourth material, and the first gap passes through the third thickness, the fourth thickness, and substantially through the second thickness to terminate at the second surface.
In some embodiments of the present disclosure, the module may further include a second gap filled with the second material, where the second gap passes substantially through the first thickness to terminate at the first surface, and the second gap separates the first contact of the first cell from the first contact of the second cell. In some embodiments of the present disclosure, the module may further include a third gap, where the third gap passes through fourth thickness, the third thickness, and substantially through the second thickness to terminate at the second surface, and the third gap separates the second contact of the first cell from the second contact of the second cell. In some embodiments of the present disclosure, the module may further include an insulating layer that includes a fifth material and positioned on the second contact layer, where the second contact layer is positioned between the insulating layer and the HTL, the insulating layer is not electrically conductive, and the fifth material fills the third gap.
In some embodiments of the present disclosure, the perovskite may be defined by ABX3, where A is a first cation, B is a second cation, and X is an anion. In some embodiments of the present disclosure, the perovskite may include at least one of MAPbI3 and/or MAxFA1-xPbI3, wherein x is between zero and one, inclusively. In some embodiments of the present disclosure, the first material may include at least one of a metal nanowire, a carbon nanotube, a transparent conducting oxide, graphene, and/or PEDOT:PSS. In some embodiments of the present disclosure, the second material may include at least one of TiO2, ZnO, SnO2, BaSnO3, and/or SrTiO3. In some embodiments of the present disclosure, the ETL may have a thickness between 5 nm and 10 μm, inclusively.
In some embodiments of the present disclosure, the ETL may include a compact layer and a mesoporous layer, and the compact layer may be positioned between the mesoporous layer and the first contact layer. In some embodiments of the present disclosure, the third material may include at least one of spiro-OMeTAD, PTAA, NiO, CuSCN, CuPc, CuI, a graphene oxide, a carbon nanotube, and/or any suitable organic material. In some embodiments of the present disclosure, the fourth material may include at least one of gold, silver, copper, aluminum, nickel, chromium, a molybdenum oxide, a carbon nanotube, graphene, and/or a transparent conducting oxide. In some embodiments of the present disclosure, the second contact layer may have a thickness between 1 nm and 10 μm, inclusively. In some embodiments of the present disclosure, the fifth material may include a polymer.
An aspect of the present disclosure is a method for manufacturing a solar cell module, where the method includes a first applying of a first solution of an electron transfer layer (ETL) precursor onto a first surface of a first contact layer having a first thickness, where the first applying results in a first liquid film on the first surface, the first liquid film transforms into the ETL that includes a first solid material and having a second surface, and the first applying is performed using at least one of spin coating, spray coating, blade coating, slot-die coating, inkjet printing, screen printing, electrodeposition, sputtering, evaporation, pulsed laser deposition, chemical vapor deposition, and/or atomic layer deposition. In some embodiments of the present disclosure, the first applying may be performed by spray coating. In some embodiments of the present disclosure, the first applying may be performed by spray pyrolysis. In some embodiments of the present disclosure, during the first applying, the first surface may be at a temperature between 300° C. and 600° C. In some embodiments of the present disclosure, the ETL precursor may include titanium diisopropoxide bis(acetylacetonate).
Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting.
The present disclosure may address one or more of the problems and deficiencies of the prior art discussed above. However, it is contemplated that some embodiments as disclosed herein may prove useful in addressing other problems and deficiencies in a number of technical areas. Therefore, the embodiments described herein should not necessarily be construed as limited to addressing any of the particular problems or deficiencies discussed herein.
The present disclosure relates to PSCs suitable for full-scale use (e.g. industrial and/or commercial) and methods for manufacturing these PSCs. Large-area PSCs can be separated into smaller area sub-cells, which may then be series interconnected to form a solar module. The solar module integration avoids long distance charge transport in TCO substrates, thus reducing parasitic resistive losses. Solar module integration also increases the photo-voltage available from the modules. There are at least two approaches to constructing a solar module on a monolithic substrate. One is to deposit each functioning layer only onto the needed regions, either through a mask guided deposition or pattern-able printing techniques (e.g. screen printing). Another approach is to coat each layer on the entire substrate area and later separate the sub-cells with laser and/or mechanical scribing. Both methods generate “dead” regions depending on the resolution of the patterning or scribing methods used. The ratio of active area to substrate area is referred to as the geometric fill factor (GFF) of the module, with a higher GFF meaning a smaller dead area power loss due to the module integration. The first approach usually creates wider gap distances between sub-cells due to the lower resolution compared to the gap distances that can be achieved using laser scribing. The wider gap distances may result in erosion of the module's active area and reduced GFF of the modules.
One major difference between large-area solar modules (e.g. full-scale) and small-area single cells (e.g. lab-scale) is the contacts connecting individual sub-cells. Developing procedures to scribe sub-cells and make reliable and effective interconnections between them are of critical importance to fabricate large-scale solar modules with efficiencies as high as those demonstrated in single cells. Thus, the present disclosure demonstrates a fully scalable manufacturing method for perovskite module fabrication. In some embodiments of the present disclosure, a TiO2 electron transport layer (ETL) may be deposited using spray pyrolysis, with both a perovskite absorber layer and a spiro-OMeTAD hole transport layer (HTL) deposited using blade coating. The influence of TiO2 ETL thickness on the resistance of metal/TiO2/TCO interconnections in the resultant perovskite modules are described herein. The optimized ETL thickness to balance shunting and interconnection resistance is identified. With optimizations on the ETL thickness, blade coating HTL, and perovskite composition, an aperture PCE of 15.6% and an aperture area of 10.36 cm2 was achieved for a 4-cell perovskite module, with the cells in series, with gaps (the result of scribing) separating the individual cells from one another. This example is among the highest efficiencies of perovskite solar modules fabricated by scalable deposition methods.
The term “spray pyrolysis” refers in general to a process in which thins films may be deposited by spraying a solution containing precursors onto a heated surface, where the precursors react and/or thermally degrade to form the desired films, for example TiO2. In some embodiments of the present disclosure, the precursors for forming TiO2 (titanium diisopropoxide bis(acetylacetonate) in a 1-butanol solution) may be sprayed onto a heated substrate (e.g. glass) that is at a temperature between 300° C. and 600° C., or between 400° C. and 550° C. Further, the terms “mesoporous” layers and “compact” layers refer to the presence or absence, respectively, of pores in the layers. In some embodiments of the present disclosure, a mesoporous TiO2 film (e.g. ETL film) may be formed from a plurality of interconnected TiO2 nanoparticles having a characteristic length between 50 nm and 100 nm, wherein the interconnected nanoparticles also contain interstitial spaces, or pores, resulting in an overall empty volume in the film between 50% and 70%. In contrast, a compact TiO2 film, formed for example by vapor phase deposition, has an overall empty pore volume equal to zero percent, or approaching zero percent.
Thus, in some embodiments of the present disclosure, one or more layers (e.g. a perovskite layer and/or a HTL) of a solar cell module may be deposited by blade coating. Blade coating may be performed at a speed between 0.05 meters/minute and 1000 m/min, or between 0.25 m/min and 300 m/min. Further, blade coating may be performed at a height between 40 μm and 400 μm, or between 25 μm and 200 μm. In some embodiments of the present disclosure, blade coating may apply a liquid precursor such that the applied liquid film has a wet film thickness between 1 μm and 20 μm, corresponding to a liquid precursor application rate between 1 ml/m2 and 20 ml/m2, or between 0.1 ml/m2 and 50 ml/m2.
Typical inorganic perovskites include calcium titanium oxide (calcium titanate) minerals such as, for example, CaTiO3 and SrTiO3. In some embodiments of the present invention, the A-cation 110 may include a nitrogen-containing organic compound such as an alkyl ammonium compound. The B-cation 120 may include a metal and the X-anion 130 may include a halogen. Additional examples for the A-cation 110 include organic cations and/or inorganic cations, for example Cs, Rb, K, Na, Li, and/or Fr. Organic A-cations 110 may be an alkyl ammonium cation, for example a C1-20 alkyl ammonium cation, a C1-6 alkyl ammonium cation, a C2-6 alkyl ammonium cation, a C1-5 alkyl ammonium cation, a C1-4 alkyl ammonium cation, a C1-3 alkyl ammonium cation, a C1-2 alkyl ammonium cation, and/or a C1 alkyl ammonium cation. Further examples of organic A-cations 110 include methylammonium (CH3NH3+), ethylammonium (CH3CH2NH3+), propylammonium (CH3CH2 CH2NH3+), butylammonium (CH3CH2 CH2 CH2NH3+), formamidinium (NH2CH═NH2+), hydrazinium, acetylammonium, dimethylammonium, imidazolium, guanidinium and/or any other suitable nitrogen-containing or organic compound. In other examples, an A-cation 110 may include an alkylamine. Thus, an A-cation 110 may include an organic component with one or more amine groups. For example, an A-cation 110 may be an alkyl diamine halide such as formamidinium (CH(NH2)2). Thus, the A-cation 110 may include an organic constituent in combination with a nitrogen constituent. In some cases, the organic constituent may be an alkyl group such as straight-chain or branched saturated hydrocarbon group having from 1 to 20 carbon atoms. In some embodiments, an alkyl group may have from 1 to 6 carbon atoms. Examples of alkyl groups include methyl (C1), ethyl (C2), n-propyl (C3), isopropyl (C3), n-butyl (C4), tert-butyl (C4), sec-butyl (C4), iso-butyl (C4), n-pentyl (C5), 3-pentanyl (C5), amyl (C5), neopentyl (C5), 3-methyl-2-butanyl (C5), tertiary amyl (C5), and n-hexyl (C6). Additional examples of alkyl groups include n-heptyl (C7), n-octyl (C8) and the like.
Examples of metal B-cations 120 include, for example, lead, tin, germanium, and or any other 2+ valence state metal that can charge-balance the perovskite 100. Further examples include transition metals in the 2+ state such as Mn, Mg, Zn, Cd, and/or lanthanides such as Eu. B-cations may also include elements in the 3+ valence state, as described below, including for example, Bi, La, and/or Y. Examples for X-anions 130 include halogens: e.g. fluorine, chlorine, bromine, iodine and/or astatine. In some cases, a perovskite may include more than one X-anion 130, for example pairs of halogens; chlorine and iodine, bromine and iodine, and/or any other suitable pairing of halogens. In other cases, the perovskite halide 100 may include two or more halogens of fluorine, chlorine, bromine, iodine, and/or astatine.
Thus, the A-cation 110, the B-cations 120, and X-anion 130 may be selected within the general formula of ABX3 to produce a wide variety of perovskites 100, including, for example, methylammonium lead triiodide (CH3NH3PbI3), and mixed halide perovskites such as CH3NH3PbI3-xClx and CH3NH3PbI3-xBrx. Thus, a perovskite 100 may have more than one halogen element, where the various halogen elements are present in non-integer quantities; e.g. x is not equal to 1, 2, or 3. In addition, perovskites can form three-dimensional (3-D), two-dimensional (2-D), one-dimensional (1-D) or zero-dimensional (0-D) networks, possessing the same unit structure. As described herein, the A-cation 110 of a perovskite 100, may include one or more A-cations, for example, one or more of cesium, FA, MA, etc. Similarly, the B-cation 120 of a perovskite 100, may include one or more B-cations, for example, one or more of lead, tin, germanium, etc. Similarly, the anion 130 of a perovskite 100 may include one or more anions, for example, one or more halogens. Any combination is possible provided that the charges balance.
For example, a perovskite having the basic crystal structure illustrated in
Each cell (202A and 202B) may be positioned on a substrate 210. The substrate 210 may be constructed of any suitable material including at least one of glass, foil and/or plastic. A substrate 210 may have a thickness between several micrometers and several millimeters. A first contact layer 220, for example a transparent conducting oxide (TCO) layer, may be positioned in direct physical contact with the substrate 210. TCOs may include at least one of fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), indium zinc oxide (IZO), gallium zinc oxide (GZO), and/or aluminum-doped zinc oxide (AZO). In some embodiments of the present disclosure, a transparent first contact layer 220 may be in the form of at least one of a metal nanowire, a carbon nanotube, a p-type transparent conducting layer, a CuS-based TCO, PEDOT:PSS, and/or a graphene sheet. Gaps (270, 280, and 290) may separate the first contact layer 220 into different sections (e.g. 220A and 220B) corresponding to TCO sections for each respective cell. Each gap (270, 280, and 290) may have a width between about 1 μm and about 1 mm, or between about 5 μm to 250 μm. The module 200 may also include an electron transport layer (ETL) 230 positioned in contact with the first contact layer 220 (e.g. a TCO), such that the first contact layer 220 may be positioned between the substrate 210 and the ETL 230. The ETL 230 shown in
An ETL 230 may be constructed of at least one of TiO2, ZnO, SnO2, BaSnO3, and/or SrTiO3, having a thickness between about 5 nm and about 1 μm. In some embodiments of the present disclosure, an ETL 230 may include a first compact layer of these materials and a second mesoporous layer of these materials. Each cell (202A and 202B) of the module 200 may contain a perovskite layer 240, for example an organic-inorganic halide perovskite, as an active layer. So, each cell (202A and 202B) may have its own respective perovskite layer (240A and 240B), positioned in direct physical contact with the underlying ETL 230. The perovskite layer 240 may be constructed of any suitable perovskite having a crystal structure as illustrated in
The ideal example of a module 200, shown in
Finally, the ideal module 200, as shown in
Referring again to
Referring again to
The fifth intermediate module, having a HTL 250, may then be processed by the forming of a second gap 345 onto the surface of the HTL 250; e.g. patterning by laser scribing, mechanical etching, and/or chemical etching. Thus, the forming of the second gap 345 may result in a sixth intermediate module 347 having a patterned HTL 250, having one or more second gaps. The patterning may completely penetrate the thickness of the HTL 250, the thickness of the underlying perovskite layer 240, and the thickness of the underlying ETL 230. Subsequent to the forming of the second gap 345, the sixth intermediate module 347 having a patterned HTL surface may be processed by the depositing of a second contact layer 350 onto the patterned surface of the HTL 250. The depositing of the second contact layer 350 may be accomplished by at least one of thermal evaporation, spin coating, spray coating, blade coating, slot-die coating, inkjet printing, screen printing, sputtering, PLD, CVD, and/or ALD, at a temperature between about room temperature and about 350° C., resulting in the forming of a seventh intermediate module 352. The second contact layer 260 may completely fill the second gaps, resulting in the ETL filled gaps 290 shown in
Finally, the method 300 may conclude with the forming of a third gap 355 (the empty gap 270 of
In some embodiments of the present disclosure, a (n-i-p) PSC architecture includes a stack of device layers glass/TCO/ETL/perovskite/HTL/metal, corresponding to substrate/first contact layer/ETL/perovskite layer/HTL/second contact layer. The ETL and the HTL may be constructed of TiO2 and doped spiro-OMeTAD, respectively. The physical properties of the TiO2 ETL (e.g., thickness, roughness, porosity, and conductivity) may strongly influence the device performance as well as the hysteresis behavior largely due to the effects of the ETL on the kinetics of electron extraction. In general, an ETL should be pinhole free to minimize shunting and to enable selective/effective extraction and conduction of electrons away from the perovskite layer. The ETL thickness may need to be optimized for high-efficiency PSCs. In some embodiments of the present disclosure, spray-pyrolysis coating may be used to deposit compact TiO2 (c-TiO2) ETLs onto a device. In some embodiments of the present disclosure, the thickness of a TiO2 layer (between 1 nm and 100 nm) may be defined by controlling at least one of the number of coating cycles, the rate of spraying, the concentration of the TiO2 precursor, and/or the total spray volume of the TiO2 precursor (see
The TiO2 (ETL) film thickness significantly affected PV performances, with large differences in performances evident between the larger perovskite modules and the smaller lab-scale devices (˜0.1 cm2 active area). The statistics of PV parameters for both modules and smaller-area devices (cells) are compared in
To understand the different TiO2 ETL thickness dependence between smaller-area cells and larger area modules, it is necessary to examine how the perovskite modules are constructed in comparison to the standard process of constructing smaller-area devices. Referring again to
Composition engineering via A-site cation alloying (e.g., methylammonium—MA, formamidinium—FA, cesium) may improve the performance of perovskite solar cells. MA-FA alloying may result in the scalable deposition of perovskite thin films when assisted with the use of a heated substrate and the adjusting of the solvent composition may provide a wide processing window for blade coating processing method to manufacture high-quality perovskite thin films. Therefore, such solvent strategies were utilized with blade coating methods for producing mixed-cation perovskites. Panels (a) and (b) of
Perovskite solar cells were prepared to compare the device characteristics. The typical J-V curves and EQE spectra of lab-scale PSCs (˜0.1 cm2 active area) using MAPbI3 and MA0.7FA0.3PbI3 are compared in
To achieve large scale production of perovskite modules, it is important to have fully scalable deposition methods for producing all device layers, including the perovskite active layer and the charge transport layers (e.g. ETL and HTL). For the PSC device structures used in this study, the TiO2 ETL was prepared by spray pyrolysis, which is scalable and suitable for large area module fabrication. In addition, as described herein, blade coating was implemented to produce a spiro-OMeTAD HTL with a composition that is also useful for application using a spin coating process. The blade coating method using the spiro-OMeTAD composition performed well. An example of the HTL solution includes 72 mg 2,2′,7,7′-tetrakis(N,N-dip-methoxyphenylamine)-9,9′-spirobifluorene (Spiro-MeOTAD; Merck), 17 μL bis(trifluoromethane) sulfonimide lithium salt stock solution (520 mg Li-TFSI in 1 mL acetonitrile), and 29 μL 4-tert-butylpyridine (TBP), 20 μL FK102 Co(III) TFSI solution (300 mg/mL in acetonitrile), and 1 mL chlorobenzene solvent.
With the capability of fully scalable deposition of a perovskite-containing device stack, a six-cell module was manufactured with a ˜26 cm2 aperture area, produced by blade coating of both the perovskite layer and HTL (see
The impact of other second contact layer materials on the contact characteristics was also evaluated, with the results summarized in
As used herein, the term “substantially” refers to the inherent error involved in any numerical measurement. For example, a gap extending substantially through a thickness of layer refers to a gap that extends exactly through the thickness, a gap that extends almost entirely through the thickness, and a gap that extends entirely through the thickness and into the underlying substrate. The exact depth of the gap for the second and third cases will depend on the method used for forming the gap, e.g. laser scribing, mechanical scribing, and/or chemical etching, and are known to one of ordinary skill in the art of scribing photovoltaic materials and surfaces.
Experimental:
Organic-Inorganic Halide Perovskite film deposition. For blade coating, 42 wt % equimolar ratio MAI and PbI2 precursors with 20% MACl additive in mixed solvent (NMP/DMF 55/45 weight ratio) were used. For mixed cations, 30% (molar ratio) FAI and 70% (molar ratio) MAI was used to replace MAI, and mixed solvent was adjusted to a higher DMF ratio (NMP/DMF 30/70 weight ratio). Blade coating was performed on a Zehntner-Automatic film applicator coater using Zehntner ZUA 2000 blade at room temperature inside a N2-filled glovebox. The gap between blade and top substrate was fixed at 130 μm and the speed of coating was 5 mm/s. Once the precursor ink was dispensed on to the substrate by blade coating, the substrate was transferred into diethyl ether bath after about one minute of drying. Perovskite film crystalized in ether bath in 1 minute. A further thermal annealing was conducted after the bath at 150° C. with petri-dish covered for 75 seconds.
Device fabrication. For small area devices, a fluorine-doped tin oxide (FTO) substrate (TEC 7, Hartford Glass Co) was patterned using hydrogen evolution etching method (zinc powder and 5M HCl solution). For larger surface area modules (MMs), 1.5″×2″ TEC 7 substrates were laser-scribed (532 nm) with 7 mm spacing. Pre-patterned FTO was cleaned in base bath (0.2 M NaOH in ethanol) and then deposited with compact TiO2 (c-TiO2) layers of various thickness by spray pyrolysis using 0.2 M titanium diisopropoxide bis(acetylacetonate) in a 1-butanol solution at 450° C. The thickness of TiO2 was controlled by the amount of sprayed solvent. Sprayed film was annealed at 450° C. for 1 hour. A thin C60 layer was deposited on the top of c-TiO2. The concentrations of C60 SAM (1-material) were 1-1.5 mg/ml in mixed solvent (chlorobenzene/tetrahydrofuran=1/1 volume ratio). Blade coating was done with 2.5 mm/s speed with 130 μm gap and spin coating was done are 4000 rpm for 30 seconds. The perovskite film was subsequently coated before the deposition of the hole transport layer (HTL). The HTL solution was composed of 72 mg 2,2′,7,7′-tetrakis(N,N-dip-methoxyphenylamine)-9,9′-spirobifluorene (Spiro-MeOTAD; Merck), 17 μL bis(trifluoromethane) sulfonimide lithium salt stock solution (520 mg Li-TFSI in 1 mL acetonitrile), and 29 μL 4-tert-butylpyridine (TBP), 20 μL FK102 Co(III) TFSI solution (300 mg/mL in acetonitrile), and 1 mL chlorobenzene solvent. HTL was spin coated at 4,000 rpm for 35 seconds or blade coated at 130 μm gap with 10 mm/s speed. For MMs, the P2 gaps were scribed next to the P1 gaps using a mechanical scriber. A 100-nm Au layer was deposited on the HTL layer by thermal evaporation for top contact. For MMs, the P3 gaps were further performed next to the P2 gaps to isolate top contacts. Edges of MMs were further deleted, and copper foil tape was attached for external wiring.
Film characterizations. X-ray diffraction (XRD) of the perovskite thin films was performed using an X-ray diffractometer (Rigaku D/Max 2200) with Cu Ka radiation. Absorption spectra were carried out by an ultraviolet-visible (UV/Vis) spectrometer (Cary-6000i). SEM was taken by NOVA 630 NanoSEM, FEI. Contact resistance measurement was conducted on FTO/c-TiO2/Au sandwiched structure using Keithley Source Meter (Model 2400) under one-sun condition.
Device characterizations. The J-V characteristics of the cells were obtained by using a Keithley Source Meter (Model 2400) under simulated one-sun AM 1.5G illumination at 100 mW cm −2 (Oriel Sol3A Class AAA Solar Simulator, Newport Corporation). A non-reflective shadow mask was used to define active area (0.12 cm2 for small area and 10.36 cm2 for MMs unless otherwise stated). External quantum efficiency (EQE) was measured using a solar cell quantum efficiency measurement system (QEX10, PV Measurements). Stabilized power output was monitored by a potentiostat (VersaSTAT MC, Princeton Applied Research) near a maximum power output point.
A perovskite-containing solar cell module comprising: a glass substrate; a first cell; and a second cell, wherein: each cell comprises, in order: a first contact layer comprising fluorine-doped tin oxide, positioned on the substrate, and having an outside surface and a first thickness; an electron transfer layer comprising TiO2 and having a second thickness between 1 nm and 10 μm; an active layer comprising the perovskite and having a third thickness; a hole transfer layer comprising Spiro-OMeTAD and having a fourth thickness; and a second contact layer comprising copper and having a fifth thickness, the first cell and the second cell are electrically connected by a first gap filled with the copper, and the first gap passes through the third thickness, the fourth thickness, and substantially through the second thickness to terminate at the outside surface.
A perovskite-containing solar cell module comprising: a substrate having a first surface;
a first cell; and a second cell, wherein: each cell comprises, in order: a first contact layer comprising a first material, positioned on the substrate, and having a second surface and a first thickness; an electron transfer layer (ETL) comprising a second material and having a second thickness; an active layer comprising the perovskite and having a third thickness; a hole transfer layer (HTL) comprising a third material and having a fourth thickness; and a second contact layer comprising a fourth material and having a fifth thickness, the first cell and the second cell are electrically connected by a first gap filled with the fourth material, and the first gap passes through the third thickness, the fourth thickness, and substantially through the second thickness to terminate at the second surface.
The solar cell module of Example 2, further comprising: a second gap filled with the second material, wherein: the second gap passes substantially through the first thickness to terminate at the first surface, and the second gap separates the first contact of the first cell from the first contact of the second cell.
The solar cell module of either Example 2 or 3, further comprising: a third gap, wherein the third gap passes through fourth thickness, the third thickness, and substantially through the second thickness to terminate at the second surface, and the third gap separates the second contact of the first cell from the second contact of the second cell.
The solar cell module of any one of Examples 2-4, further comprising: an insulating layer comprising a fifth material and positioned on the second contact layer, wherein: the second contact layer is positioned between the insulating layer and the HTL, the insulating layer is not electrically conductive, and the fifth material fills the third gap.
The solar cell module of any one of Examples 2-5, wherein: the perovskite is defined by ABX3, A is a first cation, B is a second cation, and X is an anion.
The solar cell module of any one of Examples 2-6, wherein the first cation comprises at least one of an alkyl ammonium, formamidinium (FA), or cesium.
The solar cell module of any one of Examples 2-7, wherein the first cation comprises at least one of methylammonium (MA) or FA.
The solar cell module of any one of Examples 2-8, wherein the second cation comprises a metal.
The solar cell module of any one of Examples 2-9, wherein the metal comprises at least one of lead, tin, germanium, manganese, magnesium, zinc, cadmium, or a lanthanide.
The solar cell module of any one of Examples 2-10, wherein the anion comprises a halogen.
The solar cell module of any one of Examples 2-11, wherein the perovskite comprises at least one of MAPbI3 or MAxFA1-xPbI3, wherein x is between zero and one, inclusively.
The solar cell module of any one of Examples 2-12, wherein the active layer is applied by a solution method.
The solar cell module of any one of Examples 2-13, wherein the solution method comprises blade coating.
The solar cell module of any one of Examples 2-14, wherein the first material comprises at least one of a metal nanowire, a carbon nanotube, a transparent conducting oxide, graphene, or PEDOT:PSS.
The solar cell module of any one of Examples 2-15, wherein the transparent conducting oxide comprises at least one of a fluorine-doped tin oxide, an indium-doped tin oxide, indium zinc oxide, gallium zinc oxide, or an aluminum-doped zinc oxide.
The solar cell module of any one of Examples 2-16, wherein the second material comprises oxygen.
The solar cell module of any one of Examples 2-17, wherein the second material comprises at least one of TiO2, ZnO, SnO2, BaSnO3, or SrTiO3.
The solar cell module of any one of Examples 2-18, wherein the ETL has a thickness between 5 nm and 10 μm.
The solar cell module of any one of Examples 2-19, wherein the ETL has a thickness between 5 nm and 1 μm.
The solar cell module of any one of Examples 2-20, wherein: the ETL further comprises a compact layer and a mesoporous layer, and the compact layer is positioned between the mesoporous layer and the first contact layer.
The solar cell module of any one of Examples 2-21, wherein the ETL is applied by a solution method.
The solar cell module of any one of Examples 2-22 wherein the solution method comprises spray pyrolysis.
The solar cell module of any one of Examples 2-23, wherein the third material comprises at least one of spiro-OMeTAD, PTAA, NiO, CuSCN, CuPc, CuI, a graphene oxide, a carbon nanotube, or any suitable organic material.
The solar cell module of any one of Examples 2-24, wherein the HTL is applied by a solution method.
The solar cell module of any one of Examples 2-25, wherein the solution method comprises blade coating.
The solar cell module of any one of Examples 2-26, wherein the fourth material comprises at least one of gold, silver, copper, aluminum, nickel, chromium, a molybdenum oxide, a carbon nanotube, graphene, or a transparent conducting oxide.
The solar cell module of any one of Examples 2-27, wherein the second contact layer has a thickness between 1 nm and 10 μm.
The solar cell module of any one of Examples 2-28, wherein the fifth material comprises a polymer.
A method for manufacturing a solar cell module, the method comprising: a first applying of a first solution of an electron transfer layer (ETL) precursor onto a first surface of a first contact layer having a first thickness, wherein: the first applying results in a first liquid film on the first surface, the first liquid film transforms into the ETL comprising a first solid material and having a second surface, and the first applying is performed using at least one of spin coating, spray coating, blade coating, slot-die coating, inkjet printing, screen printing, electrodeposition, sputtering, evaporation, pulsed laser deposition, chemical vapor deposition, or atomic layer deposition.
The method of Example 30, wherein the first applying is performed by spray coating.
The method of either Example 30 or 31, wherein the first applying is performed by spray pyrolysis.
The method of any one of Examples 30-32, wherein, during the first applying, the first surface is at a temperature between 300° C. and 600° C.
The method of any one of Examples 30-33, wherein the ETL precursor comprises titanium diisopropoxide bis(acetylacetonate).
The method of any one of Examples 30-34, wherein the first solution comprises the titanium diisopropoxide bis(acetylacetonate) and a solvent.
The method of any one of Examples 30-35, wherein the solvent comprises butanol.
The method of any one of Examples 30-36, wherein the first applying is performed at a rate between 0.005 mL/cm2 to 0.5 mL/cm2.
The method of any one of Examples 30-37, wherein the first solid material comprises TiO2.
The method of any one of Examples 30-38, wherein the ETL has a second thickness between 1 nm and 100 nm.
The method of any one of Examples 30-39, wherein the second thickness between 1 nm and 10 nm.
The method of any one of Examples 30-40, wherein the first solid material is mesoporous.
The method of any one of Examples 30-41, further comprising a substrate, wherein the first contact layer is positioned between the substrate and the ETL.
The method of any one of Examples 30-42, further comprising, prior to the first applying, a first forming of a first gap, wherein the first gap passes substantially through the first thickness.
The method of any one of Examples 30-43, wherein the first forming is performed by at least one of mechanical scribing, laser scribing, or mechanical etching.
The method of any one of Examples 30-44, wherein the first gap has a width between 1 μm and 1 mm.
The method of any one of Examples 30-45, wherein: during the first applying, the first gap is filled with the ETL precursor, and after the first applying, the first gap is filled with the first solid material.
The method of any one of Examples 30-46, further comprising: after the first applying, a second applying of an active layer precursor solution onto the second surface, wherein: the second applying results in a second liquid film on the second surface.
The method of any one of Examples 30-47, wherein the active layer precursor solution comprises at least one of methylammonium iodide (MA), methylammonium chloride (MACI), formamidinium (FA), or lead iodide (PbI2).
The method of any one of Examples 30-48, wherein the active layer precursor solution further comprises a polar solvent.
The method of any one of Examples 30-49, wherein the polar solvent comprises at least one of N-Methyl-2-pyrrolidone (NMP) or dimethylformamide (DMF).
The method of any one of Examples 30-50, wherein, during the second applying, the second liquid film transforms into an active layer.
The method of any one of Examples 30-51, further comprising: a first treating, wherein: the first treating transforms the second liquid film into an active layer by removing the polar solvent, and the active layer has a third thickness and a third surface.
The method of any one of Examples 30-52, wherein the first treating comprises at least one of thermal treating, liquid-liquid extraction, or exposure of the second liquid film to a gas.
The method of any one of Examples 30-53, wherein the thermal treating comprises heating the second liquid film to a temperature between 30° C. and 100° C.
The method of any one of Examples 30-54, wherein the liquid-liquid extraction comprises submerging the second liquid film in an extracting solvent, such that the polar solvent is transferred from the second liquid film to the extracting solvent.
The method of any one of Examples 30-55, wherein the extracting solvent comprises diethyl ether.
The method of any one of Examples 30-56, wherein the active layer comprises a perovskite having the composition ABX3, where A is a first cation, B is a second cation, and X is an anion.
The method of any one of Examples 30-57, wherein the first cation comprises at least one of an alkyl ammonium, formamidinium (FA), or cesium.
The method of any one of Examples 30-58, wherein the first cation comprises at least one of methylammonium (MA) or FA.
The method of any one of Examples 30-59, wherein the second cation comprises a metal.
The method of any one of Examples 30-60, wherein the metal comprises at least one of lead, tin, germanium, manganese, magnesium, zinc, cadmium, or a lanthanide.
The method of any one of Examples 30-61, wherein the anion comprises a halogen.
The method of any one of Examples 30-62, wherein the perovskite comprises at least one of MAPbI3 or MAxFA1-xPbI3, wherein x is between zero and one, inclusively.
The method of any one of Examples 30-63, wherein the second applying is performed by at least one of spraying, blade coating, curtain coating, dip coating, spin coating, slot-die coating, inkjet printing, or screen printing.
The method of any one of Examples 30-64, wherein the second applying is performed by blade coating.
The method of any one of Examples 30-65, wherein the blade coating is performed at a speed between 0.05 meters per min (m/min) and 1000 m/min.
The method of any one of Examples 30-66, wherein the blade coating is performed at a blade height between 10 μm and 400 μm.
The method of any one of Examples 30-67, wherein the active layer precursor solution is applied at a rate between 0.1 ml/m2 and 50 ml/m2.
The method of any one of Examples 30-68, wherein the blade coating forms the second liquid film having a film thickness between 1 μm and 20 μm.
The method of any one of Examples 30-69, further comprising: after the second applying, a third applying of a hole transfer layer (HTL) solution onto the third surface, wherein: the third applying results in a third liquid film on the third surface.
The method of any one of Examples 30-70, wherein the HTL solution comprises at least one of spiro-OMeTAD, PTAA, NiO, CuSCN, CuPc, graphene oxide, carbon nanotubes, or CuI.
The method of any one of Examples 30-71, wherein the HTL solution comprises spiro-OMeTAD.
The method of any one of Examples 30-72, wherein the HTL solution further comprises at least one of bis(trifluoromethane) sulfonimide, or 4-tert-butylpyridine.
The method of any one of Examples 30-73, wherein the HTL solution further comprises a solvent.
The method of any one of Examples 30-74, wherein the solvent comprises at least one of acetonitrile or chlorobenzene.
The method of any one of Examples 30-75, wherein, during the third applying, the third liquid film transforms into a HTL.
The method of any one of Examples 30-76, further comprising: a second treating, wherein: the second treating transforms the third liquid film into a HTL by removing the solvent, and the HTL has a fourth thickness and a fourth surface.
The method of any one of Examples 30-77, wherein the second treating comprises at least one of thermal treating, liquid-liquid extraction, or exposure of the second liquid film to a gas.
The method of any one of Examples 30-78, wherein the thermal treating comprises heating the third liquid film to a temperature between 30° C. and 100° C.
The method of any one of Examples 30-79, wherein the third applying is performed by at least one of spraying, blade coating, curtain coating, dip coating, spin coating, slot-die coating, inkjet printing, or screen printing.
The method of any one of Examples 30-80, wherein the third applying is performed by blade coating.
The method of any one of Examples 30-81, wherein the blade coating is performed at a speed between 0.05 meters per min (m/min) and 1000 m/min.
The method of any one of Examples 30-82, wherein the blade coating is performed at a blade height between 10 μm and 400 μm.
The method of any one of Examples 30-83, wherein the HTL precursor solution is applied at a rate between 0.1 ml/m2 and 50 ml/m2.
The method of any one of Examples 30-84, wherein the blade coating forms the third liquid film having a film thickness between 1 μm and 20 μm.
The method of any one of Examples 30-85, further comprising, after the second treating, a second forming of a second gap, wherein the second gap passes substantially through the third thickness and substantially through the second thickness.
The method of any one of Examples 30-86, wherein the second forming is performed by at least one of mechanical scribing, laser scribing, or mechanical etching.
The method of any one of Examples 30-87, wherein the second gap has a width between 1 μm and 1 mm.
The method of any one of Examples 30-88, further comprising, after the second forming, a fourth applying of a second contact layer comprising a second solid material onto the fourth surface, wherein the second contact layer has a fifth surface.
The method of any one of Examples 30-89, wherein the second solid material fills the second gap.
The method of any one of Examples 30-90, wherein the third applying is performed by a vapor deposition method.
The method of any one of Examples 30-91, wherein the vapor deposition method is thermal evaporation.
The method of any one of Examples 30-92, wherein the second material comprises a metal.
The method of any one of Examples 30-93, wherein the metal comprises at least one of gold, silver, or copper.
The method of any one of Examples 30-94, further comprising, after the fourth applying, a third forming of a third gap, wherein the third gap passes substantially through the third thickness and the fourth thickness and substantially through the second thickness.
The method of any one of Examples 30-95, wherein the fourth forming is performed by at least one of mechanical scribing, laser scribing, or mechanical etching.
The method of any one of Examples 30-96, wherein the third gap has a width between 1 μm and 1 mm.
The method of any one of Examples 30-97, further comprising after the third forming, a fifth applying of an insulating layer comprising a third solid material onto the fifth surface.
The method of any one of Examples 30-98, wherein the insulating layer comprises a polymer.
The method of any one of Examples 30-99, wherein the third solid material fills the third gap.
The foregoing discussion and examples have been presented for purposes of illustration and description. The foregoing is not intended to limit the aspects, embodiments, or configurations to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the aspects, embodiments, or configurations are grouped together in one or more embodiments, configurations, or aspects for the purpose of streamlining the disclosure. The features of the aspects, embodiments, or configurations, may be combined in alternate aspects, embodiments, or configurations other than those discussed above. This method of disclosure is not to be interpreted as reflecting an intention that the aspects, embodiments, or configurations require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment, configuration, or aspect. While certain aspects of conventional technology have been discussed to facilitate disclosure of some embodiments of the present invention, the Applicants in no way disclaim these technical aspects, and it is contemplated that the claimed invention may encompass one or more of the conventional technical aspects discussed herein. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate aspect, embodiment, or configuration.
This application claims the benefit of U.S Provisional Patent Application No. 62/567,826 filed Oct. 4, 2017, the contents of which are incorporated herein by reference in their entirety.
The United States Government has rights in this disclosure under Contract No. DE-AC36-08GO28308 between the United States Department of Energy and Alliance for Sustainable Energy, LLC, the Manager and Operator of the National Renewable Energy Laboratory.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US18/54370 | 10/4/2018 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62567826 | Oct 2017 | US |
