Perovskite photoelectric conversion semiconductor element

Abstract

The present invention provides a perovskite photoelectric conversion semiconductor element. [Solution] A perovskite light-absorbing semiconductor element according to one embodiment of the present invention includes a substrate, a first electrode formed on the substrate, an electron transport layer formed on the first electrode, a perovskite light-absorbing semiconductor layer formed on the electron transport layer, a hole transport layer formed on the perovskite light-absorbing semiconductor layer, and a second electrode formed on the hole transport layer, wherein the first electrode has a first pitch, the electron transport layer, the perovskite light-absorbing semiconductor layer, and the hole transport layer have a second pitch, and the electron transport layer includes electron transport layer residue at the second pitch.

Description

Technical Field

[0001] The present invention relates to a perovskite photoelectric conversion semiconductor device.

Background Art

[0002] Large-area perovskite photoelectric conversion semiconductor devices have not yet been put into practical use and remain at the research stage. To form a large-area device, it is necessary to form multiple thin films on a glass substrate and then perform a patterning process to separate them. Here, the most commonly used structure in the prior art is the monolithic pattern structure.

[0003] The monolithic pattern structure is a form in which long and thin cells are connected in series through a patterning process on a large-area glass substrate when manufacturing a module of a large-area photoelectric conversion semiconductor device.

[0004] To form the monolithic pattern structure, a total of three patterning processes (etching processes) are performed. First, the patterning process P1 patterns the transparent electrode placed on the glass substrate, and generally uses an etching process using a laser.

[0005] The second patterning process P2 patterns at least three layers composed of an electron transport layer (or hole transport layer) / perovskite layer / hole transport layer (or electron transport layer). Here, a laser scribing or mechanical scribing process can be used.

[0006] Finally, the third patterning process P3 etches the electron transport layer (or hole transport layer) / perovskite layer / hole transport layer (or electron transport layer) / upper electrode after forming the upper electrode. Here, a laser scribing or mechanical scribing process is also used.

[0007] The P2 and P3 etching processes, when using a laser, require a constant thickness for the etched layer. This means that the same process conditions cannot be used when the material is changed, necessitating a post-processing step to establish new conditions. Furthermore, they require the use of expensive lasers (short wavelength and short pulse width), leading some to prefer patterning processes using mechanical etching.

[0008] When performing the process using laser etching or mechanical methods, particularly in the P2 etching process, only a minimum of three layers—the electron transport layer (or hole transport layer), perovskite thun, and hole transport layer (or electron transport layer)—must be etched, excluding the transparent electrode. However, excessive etching can cause significant damage to the multilayer thin film.

[0009] The aforementioned background technologies are those that the inventors possessed or acquired in the process of deriving the disclosures of the present invention, and are not necessarily publicly known technologies that were made available to the general public prior to this application. [Overview of the project] [Problems that the invention aims to solve]

[0010] The present invention aims to solve the above problems, and the object of the present invention is to provide a perovskite photoelectric conversion semiconductor device that does not damage the multilayer thin film by including a part of the electron transfer layer or hole transfer layer having the minimum thickness and minimum area ratio, thereby avoiding excessive etching processes.

[0011] However, the problems that this invention aims to solve are not limited to those mentioned above, and further problems not mentioned can be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0012] A perovskite photoelectric conversion semiconductor element according to one embodiment of the present invention includes a substrate, a first electrode formed on the substrate, an electron transfer layer formed on the first electrode, a perovskite light-absorbing semiconductor layer formed on the electron transfer layer, a hole transfer layer formed on the perovskite light-absorbing semiconductor layer, and a second electrode formed on the hole transfer layer, wherein the first electrode has a first pitch, the electron transfer layer, the perovskite light-absorbing semiconductor layer, and the hole transfer layer have a second pitch, and the electron transfer layer includes electron transfer layer residue at the second pitch.

[0013] A perovskite photoelectric conversion semiconductor element according to another embodiment of the present invention includes a substrate, a first electrode formed on the substrate, a hole transfer layer formed on the first electrode, a perovskite light-absorbing semiconductor layer formed on the hole transfer layer, an electron transfer layer formed on the perovskite light-absorbing semiconductor layer, and a second electrode formed on the electron transfer layer, wherein the first electrode has a first pitch, the hole transfer layer, the perovskite light-absorbing semiconductor layer, and the electron transfer layer have a second pitch, and the hole transfer layer includes hole transfer layer residue at the second pitch.

[0014] In one embodiment, the electron transport layer residue or the hole transport layer residue may have a thickness range of 0.1 nm to 2 nm.

[0015] In one embodiment, the electron transport layer residue or the hole transport layer residue may be included on the first electrode of the second pitch as an area of ​​0.05% to 99%.

[0016] In one embodiment, the electron transport layer residue or the hole transport layer residue can be formed locally.

[0017] In one embodiment, the electron transport layer residue or the hole transport layer residue can be formed by laser patterning, mechanical scribing, or both.

[0018] In one embodiment, the electron transport layer or the hole transport layer can be formed to cover at least a part of the first electrode and the substrate.

[0019] In one embodiment, the second electrode can be formed to cover at least a part of the first electrode, the electron transport layer, the perovskite light-absorbing semiconductor layer, and the hole transport layer.

[0020] In one embodiment, a third pitch can be formed in the electron transport layer, the hole transport layer, the perovskite light-absorbing semiconductor layer, and the second electrode.

[0021] In one embodiment, the first electrode, the second electrode, or both of them may be a transparent electrode or a metal electrode.

[0022] In one embodiment, the transparent electrode can include one or more selected from the group consisting of ITO, FTO, SnO2, Al:ZnO, B;ZnO, graphene, PEDOT:PSS, Ag nanowire, graphene, and carbon nanotube.

[0023] In one embodiment, the metal electrode can include one or more selected from the group consisting of Au, Ag, Ni, Cu, Mo, Pt, W, Al, and their alloys.

[0024] In one embodiment, the electron transport layer can further include one or more selected from the group consisting of TiO2, SnO2, WS2, WSe2, ZnO, and C 60 and the like.

[0025] In one embodiment, the hole transport layer can further include one or more selected from the group consisting of NiO x , Spiro-OMeTAD, PTAA, P3HT, PEDOT:PSS, and self-assembled monolayer.

[0026] In one embodiment, the perovskite light absorption semiconductor layer can include a compound having a structure.

[0027] In one embodiment, A may be one or more selected from the group consisting of methylammonium, formamidinium, Cs, and Rb.

[0028] In one embodiment, B is one or more selected from the group consisting of Pb, Sn, Ge, Sb, and Bi, and X may be one or more selected from the group consisting of I, Br, and Cl.

[0029] In one embodiment, the perovskite photoelectric conversion semiconductor device is a large-area photoelectric conversion module, and several cells can be connected in series in a monolithic structure and energized.

Advantages of the Invention

[0030] The perovskite photoelectric conversion semiconductor device according to one embodiment of the present invention includes an electron transfer layer or a hole transfer layer having a minimum thickness and a minimum area ratio on a transparent electrode, and can perform a simplified process without performing an excessive etching process and without damaging other layers.

Brief Description of the Drawings

[0031] [Figure 1] It is a cross-sectional view of a perovskite photoelectric conversion semiconductor device according to one embodiment of the present invention. [Figure 2] It is an enlarged view showing the form of an electron transfer layer residue according to another embodiment of the present invention. [Figure 3] It is a cross-sectional view of a perovskite photoelectric conversion semiconductor device according to another embodiment of the present invention. [Figure 4] It is a cross-sectional view of an Au / SnO2 / ITO contact resistance measurement sample according to an embodiment of the present invention. [Figure 5] It is a graph showing a current-voltage measurement curve for evaluating the contact resistance of Au / SnO2 / ITO according to an embodiment of the present invention. [Modes for carrying out the invention]

[0032] The embodiments will be described in detail below with reference to the attached drawings. However, various modifications may be made to the embodiments, and the scope of the patent application will not be limited or restricted by such embodiments. All modifications, equivalents, or substitutes to the embodiments should be understood to be included within the scope of the patent.

[0033] The terms used in the embodiments are for illustrative purposes only and should not be construed as intended to limit them. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “includes” or “having” indicate the presence of features, figures, steps, actions, components, parts, or combinations thereof described in the specification, and should not be understood as preemptively excluding the possibility of the presence or addition of one or more other features, figures, steps, actions, components, parts, or combinations thereof.

[0034] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as those generally understood by a person of ordinary skill in the art to which this embodiment belongs. Commonly used, predefined terms should be interpreted as having the meaning consistent with their meaning in the context of the relevant art, and not as ideal or overly formal unless expressly defined herein.

[0035] Furthermore, when explaining with reference to the attached drawings, the same components will be assigned the same reference numerals regardless of the reference numerals used in the drawings, and redundant explanations will be omitted. In the description of embodiments, if a specific explanation of related prior art is deemed to unnecessarily obscure the gist of the embodiment, such detailed explanation will be omitted.

[0036] Furthermore, in describing the components of the embodiments, terms such as first, second, A, B, (a), (b), etc., may be used. These terms are used to distinguish a component from other components, and the terms do not limit the essence, order, or sequence of the component in question.

[0037] Components included in any one embodiment and components with common functions will be described using the same names in the other embodiments. Unless otherwise stated, the descriptions in any one embodiment can be applied to the other embodiments, and specific descriptions will be omitted to the extent that they overlap.

[0038] The perovskite photoelectric conversion semiconductor device of the present invention will be described in detail below with reference to embodiments and drawings. However, the present invention is not limited to such embodiments and drawings.

[0039] A perovskite photoelectric conversion semiconductor element according to one embodiment of the present invention includes a substrate, a first electrode formed on the substrate, an electron transfer layer formed on the first electrode, a perovskite light-absorbing semiconductor layer formed on the electron transfer layer, a hole transfer layer formed on the perovskite light-absorbing semiconductor layer, and a second electrode formed on the hole transfer layer, wherein the first electrode has a first pitch, the electron transfer layer, the perovskite light-absorbing semiconductor layer, and the hole transfer layer have a second pitch, and the electron transfer layer includes electron transfer layer residue at the second pitch.

[0040] Figure 1 is a cross-sectional view of a perovskite photoelectric conversion semiconductor device according to one embodiment of the present invention.

[0041] Referring to Figure 1, a perovskite photoelectric conversion semiconductor element 100 according to one aspect of the present invention includes a substrate 110, a first electrode 120 formed on the substrate 110, an electron transfer layer 130 formed on the first electrode 120, a perovskite light absorption semiconductor layer 140 formed on the electron transfer layer 130, a hole transfer layer 150 formed on the perovskite light absorption semiconductor layer 140, and a second electrode 160 formed on the hole transfer layer 150.

[0042] The perovskite photoelectric conversion semiconductor device in Figure 1 has an NIP structure.

[0043] The substrate 110 may include a substrate made of glass or a flexible plastic. For example, the substrate 110 may be a glass substrate, a plastic substrate containing at least one selected from the group consisting of PET (polyethylene terephthalate), PEN (polyethylene naphthelate), PP (polypropylene), PI (polyamide), TAC (triacetyl cellulose), and PES (polyethersulfone), or a flexible substrate containing aluminum foil, stainless steel foil, or both. However, since a flexible substrate containing aluminum foil, stainless steel foil, or both is a conductive material that conducts electricity well, in this case, an insulating layer that insulates electricity must be formed on the flexible substrate.

[0044] Any transparent substrate can be used as the substrate 110. Sunlight incident on the substrate is absorbed by the perovskite light-absorbing semiconductor layer, forming electron-hole pairs in the light-absorbing layer, from which electricity can be generated. Therefore, it is preferable to use a substrate with low haze that can allow a large amount of sunlight to be incident on it.

[0045] If the substrate 110 is not transparent, the first electrode formed on the substrate shall be a metal electrode and the second electrode shall be a transparent electrode, and the portion to which sunlight is incident shall be the portion of the second electrode.

[0046] When using a non-transparent substrate, the configuration will be TCO / Hole transfer layer or electron transfer layer / Perovskite tun / Electron transfer layer or Hole transfer layer / Metal electrode / Substrate.

[0047] The perovskite photoelectric conversion semiconductor elements 100 and 200 of the present invention have a monolithic pattern structure as large-scale perovskite photoelectric conversion semiconductor elements.

[0048] A monolithic pattern structure is a method of connecting several cells in series on a large surface, and can generally be manufactured using three thin-film patterning processes.

[0049] According to one embodiment of the present invention, the first electrode 120, the second electrode 160, or both thereof may be transparent electrodes or metal electrodes.

[0050] The first electrode 120, the second electrode 160, or both may be transparent electrodes. When transparent electrodes are used, sunlight is facilitated to enter the perovskite light-absorbing semiconductor layer.

[0051] Furthermore, the electrodes on the surface to which sunlight is incident are preferably transparent electrodes, in order to increase the amount of sunlight absorbed by the perovskite light-absorbing semiconductor layer of the present invention.

[0052] When the first electrode 120 is a metal electrode, it has the advantage of being able to manufacture a large-scale perovskite photoelectric conversion semiconductor device with a monolithic pattern structure in a substrate structure.

[0053] The first electrode 120 has the advantage of being able to be used to manufacture a large-scale perovskite photoelectric conversion semiconductor device with a monolithic pattern structure in a superstraight structure when it is a transparent electrode.

[0054] Furthermore, the first electrode 120 is preferably thinner than the substrate, and may have a thickness of 30 nm to 1500 nm.

[0055] The transparent electrode may contain one or more selected from the group consisting of ITO, FTO, SnO2, Al:ZnO, B, ZnO and graphene, PEDOT:PSS, Ag nanowires, graphene, and carbon nanotubes (CNTs).

[0056] The metal electrode may include one or more materials selected from the group consisting of Au, Ag, Ni, Cu, Mo, Pt, W, Al, and their alloys. However, the metal electrode is not limited to the materials mentioned above, and many metallic materials can all be used.

[0057] Preferably, the transparent electrode may be ITO or FTO, and the metal electrode may be Ag, Au, or molybdenum.

[0058] According to one embodiment of the present invention, the first electrode 120 has a first pitch P1 formed thereon, and the electron transfer layer 130 can be formed to cover the first electrode 120 and at least a portion of the substrate.

[0059] Referring to Figure 1, the formation shape of the first pitch P1 can be confirmed.

[0060] The first electrode 120 is formed on the substrate 110, and then patterned to form a first pitch. The electron transfer layer 130 can be formed on the upper and side surfaces of the first electrode 120, as well as on the upper surface of the substrate 110 exposed by the first pitch.

[0061] Here, the electron transfer layer 130 can maintain a constant thickness, preferably having a thickness of 10 nm to 500 nm. The optimal thickness varies depending on the material and device structure, but generally, when the thickness of the electron transfer layer 130 is less than 10 nm, the film thickness is not constant, and when the thickness exceeds 500 nm, the resistance becomes too high.

[0062] The electron transport layer 130, the perovskite light-absorbing semiconductor layer 140, and the hole transport layer 150 have a second pitch P2 formed thereon, and the second electrode 160 can be formed to cover at least a portion of the first electrode 120, the electron transport layer 130, the perovskite light-absorbing semiconductor layer 140, and the hole transport layer 150.

[0063] The second pitch is formed by patterning an electron transport layer 130, a perovskite light-absorbing semiconductor layer 140, and a hole transport layer 150 for current flow between separated cells.

[0064] The second pitch includes the electron transport layer residue 132.

[0065] In one embodiment, the electron transfer layer residue 132 may have a thickness in the range of 0.1nm to 2nm, 0.1nm to 1.8nm, 0.1nm to 1.5nm, 0.1nm to 1.3nm, 0.1nm to 1nm, 0.1nm to 0.8nm, 0.1nm to 0.5nm, 0.1nm to 0.3nm, 0.5nm to 2nm, 0.5nm to 1.8nm, 0.5nm to 1.5nm, 0.5nm to 1.3nm, 0.5nm to 1nm, 0.5nm to 0.8nm, 1nm to 2nm, 1nm to 1.8nm, 1nm to 1.5nm, 1nm to 1.3nm, 1.5nm to 2nm, or 1.5nm to 1.8nm.

[0066] In one embodiment, the electron transport layer residue 132 is distributed on the first electrode 120 of the second pitch in the following proportions: 0.05%~99%, 0.05%~90%, 0.05%~80%, 0.05%~70%, 0.05%~60%, 0.05%~50%, 0.05%~40%, 0.05%~30%, 0.05%~20%, 0.05%~10%, 0.05%~5%, 0.05%~1%, 1%~90%, 1%~80%, 1%~70%, 1%~60%, 1%~50%, 1%~40%, 1%~30%, 1%~20% The area may remain as 1%~10%, 10%~99%, 10%~90%, 10%~80%, 10%~70%, 10%~60%, 10%~50%, 10%~40%, 10%~30%, 10%~20%, 30%~99%, 30%~90%, 30%~80%, 30%~70%, 30%~60%, 30%~50%, 30%~40%, 50%~99%, 50%~90%, 50%~80%, 50%~70%, 50%~60%, 80%~99%, 80%~90%, or 90%~99%.

[0067] Figure 2 is an enlarged view showing the morphology of the electron transport layer residue according to another embodiment of the present invention.

[0068] Referring to Figure 2, the electron transport layer residue 132 does not have a constant thickness and may be formed locally. The electron transport layer residue 132 may be formed with an irregular thickness.

[0069] In one embodiment, the electron transfer layer residue 132 can be formed by laser patterning, mechanical scribing, or both.

[0070] The aforementioned laser patterning method uses Nd:YAG (Neodymium-doped yttrium aluminum garnet; Nd:Y3Al5O 12 The laser wavelength may be 200 nm to 1064 nm, and one or more lasers may be selected from the group consisting of ), Nd:YVO4 (Neodymium-doped yttrium orthovanadate), diodes, KrF, and CO2 gas lasers.

[0071] The duration of the laser pulse used in the laser patterning method may be 100 nsec or less, and preferably 10 psec to 100 nsec.

[0072] The electron transport layer residue 132 has the advantage of strengthening the adhesion strength between the second electrode and the first electrode. Normally, when a thin film of a metal electrode (such as an Au or Ag thin film) is deposited onto a transparent electrode (the first electrode), the adhesion strength is poor due to the difference in crystal structure and surface energy of both thin films. Therefore, a method of forming a seed layer of Ti, Ni, or Cr is used to improve the adhesion strength. The electron transport layer residue 132, as an oxide series material, has higher adhesion strength compared to the metal / transparent electrode. In addition, if the electron transport layer residue is partially present, the surface area increases, further increasing the adhesion strength. If the adhesion strength is not good, there is a very high possibility that problems will arise in the long-term reliability of large-scale photoelectric conversion semiconductor devices in the future.

[0073] In laser patterning, increasing the laser energy or the number of patterning passes can completely remove electron transport layer residue, but this can cause laser damage to other multilayer thin films. Similarly, in mechanical patterning scribing, increasing the pressure applied during mechanical etching or the number of etching passes can completely remove electron transport layer residue, but this can damage transparent electrodes and glass substrates. Therefore, this method simplifies the process without inducing damage to multilayer thin films by avoiding excessive etching steps.

[0074] The second pitch is formed to allow current to flow between the perovskite light-absorbing semiconductor layers 140 of the separated cells, thereby forming positive and negative charges at opposite ends within the perovskite light-absorbing semiconductor layer 140.

[0075] More specifically, a positive charge may be formed at the interface between the perovskite light-absorbing semiconductor layer 140 and the second electrode 160, and a negative charge may be formed at the interface between the perovskite light-absorbing semiconductor layer 140 and the first electrode 120.

[0076] Furthermore, cells that are separated by a connection between the positive charge formation area of ​​the perovskite light-absorbing semiconductor layer 140 in a separated cell and the negative charge formation area of ​​the perovskite layer in an adjacent cell can be connected in series as a whole.

[0077] According to one embodiment of the present invention, the electron transport layer 130, the perovskite light-absorbing semiconductor layer 140, the hole transport layer 150, and the second electrode 160 can form a third pitch P3.

[0078] The third pitch serves to divide the photoelectric conversion module of the present invention, which is formed in a monolithic pattern structure, into cells.

[0079] The electron transfer layer 130 is made of TiO2, SnO2, WS2, WSe2, ZnO, and C 60 The Hole transmission layer further comprises one or more selected from the group consisting of NiO x It may further include one or more selected from the group consisting of Spiro-OMeTAD, PTAA, P3HT, PEDOT:PSS, and self-assembled monolayers.

[0080] The electron transport layer may contain an N-type semiconductor material, and the hole transport layer may contain a P-type semiconductor material.

[0081] According to one embodiment of the present invention, the perovskite light-absorbing semiconductor layer comprises a compound having an ABX3 structure, wherein A is one or more selected from the group consisting of methylammonium, formamidinium, Cs, and Rb, B is one or more selected from the group consisting of Pb, Sn, Ge, Sb, and Bi, and X is one or more selected from the group consisting of I, Br, and Cl.

[0082] According to one embodiment of the present invention, the perovskite light-absorbing semiconductor layer may include one or more selected from the group consisting of MAPbI3, FAPbI3, CsPbI3, MAPbBr3, FAMAPbI3, FAMAPbBr3, CsFAMAPbI3, CsFAMAPbBr3, CsFAMAPbCl3, CsFAMAPb(I,Br)3, MASnI3, FASnI3, CsSnI3, MASnBr3, FAMASnI3, FAMASnBr3, CsFAMASnI3, CsFAMASnBr3, CsFAMASnCl3, and CsFAMASn(I,Br)3.

[0083] The perovskite light-absorbing semiconductor layer, which absorbs sunlight and forms excitons, preferably has a thickness of 20 nm to 2000 nm. More preferably, the thickness of the perovskite light-absorbing semiconductor layer may be 300 nm to 600 nm. If the thickness of the light-absorbing layer is greater than the above numerical range, there is a disadvantage that electron / hole pairs must travel a longer distance, resulting in greater recombination. If the thickness is thinner than the above numerical range, there is a disadvantage that light absorption decreases, resulting in fewer electron-hole pairs being generated.

[0084] According to one embodiment of the present invention, the perovskite photoelectric conversion semiconductor element is a large-scale photoelectric conversion semiconductor module in which several cells are connected in series in a monolithic structure and can be energized.

[0085] A perovskite photoelectric conversion semiconductor element according to another embodiment of the present invention includes a substrate, a first electrode formed on the substrate, a hole transfer layer formed on the first electrode, a perovskite light-absorbing semiconductor layer formed on the hole transfer layer, an electron transfer layer formed on the perovskite light-absorbing semiconductor layer, and a second electrode formed on the electron transfer layer, wherein the first electrode has a first pitch, the hole transfer layer, the perovskite light-absorbing semiconductor layer, and the electron transfer layer have a second pitch, and the hole transfer layer includes hole transfer layer residue at the second pitch.

[0086] Figure 3 is a cross-sectional view of a perovskite photoelectric conversion semiconductor device according to another embodiment of the present invention.

[0087] The perovskite photoelectric conversion semiconductor device shown in Figure 3 has a PIN structure.

[0088] Referring to Figure 3, a perovskite photoelectric conversion semiconductor element 100' according to one aspect of the present invention includes a substrate 110, a first electrode 120 formed on the substrate 110, a hole transfer layer 150 formed on the first electrode 120, a perovskite light absorption semiconductor layer 140 formed on the hole transfer layer 150, an electron transfer layer 130 formed on the perovskite light absorption semiconductor layer 140, and a second electrode 160 formed on the electron transfer layer 130.

[0089] The perovskite photoconversion semiconductor element 100 shown in Figure 1 and the perovskite photoconversion semiconductor element 100' shown in Figure 3 differ only in the positions of the electron transport layer and the hole transport layer; the remaining configurations are identical. Therefore, the following configurations are the same as those of the perovskite photoconversion semiconductor element 100 shown in Figure 1, and the specific configurations of the substrate 110, first electrode 120, hole transport layer 150, perovskite light absorption semiconductor layer 140, electron transport layer 130, and second electrode 160 are omitted.

[0090] The first electrode 120 is formed on the substrate 110, and then patterned to form the first pitch. The hole transmission layer 150 is formed on the upper surface of the substrate 110, which is exposed by the pitch, along with the upper and side surfaces of the first electrode 120.

[0091] Here, the hole transmission layer 150 maintains a constant thickness, preferably having a thickness of 10 nm to 500 nm. The optimal thickness varies depending on the material and device structure, but generally, when the thickness of the hole transmission layer 150 is less than 10 nm, the film thickness is not constant, and when the thickness exceeds 500 nm, the resistance is too high.

[0092] The hole transfer layer 150, the perovskite light-absorbing semiconductor layer 140, and the electron transfer layer 130 have a second pitch P2 formed thereon, and the second electrode 160 is formed to cover at least a portion of the first electrode 120, the hole transfer layer 150, the perovskite light-absorbing semiconductor layer 140, and the electron transfer layer 130.

[0093] The second pitch can be formed by patterning a hole transfer layer 150, a perovskite light-absorbing semiconductor layer 140, and an electron transfer layer 130 for current flow between separated cells.

[0094] The second pitch includes the residual hole transmission layer 152.

[0095] In one embodiment, the hole transfer layer residue 152 may have a thickness range of 0.1nm to 2nm, 0.1nm to 1.8nm, 0.1nm to 1.5nm, 0.1nm to 1.3nm, 0.1nm to 1nm, 0.1nm to 0.8nm, 0.1nm to 0.5nm, 0.1nm to 0.3nm, 0.5nm to 2nm, 0.5nm to 1.8nm, 0.5nm to 1.5nm, 0.5nm to 1.3nm, 0.5nm to 1nm, 0.5nm to 0.8nm, 1nm to 2nm, 1nm to 1.8nm, 1nm to 1.5nm, 1nm to 1.3nm, 1.5nm to 2nm, or 1.5nm to 1.8nm.

[0096] In one embodiment, the hole transmission layer residue 152 is distributed on the first electrode of the second pitch in the following proportions: 0.05%~99%, 0.05%~90%, 0.05%~80%, 0.05%~70%, 0.05%~60%, 0.05%~50%, 0.05%~40%, 0.05%~30%, 0.05%~20%, 0.05%~10%, 0.05%~5%, 0.05%~1%, 1%~90%, 1%~80%, 1%~70%, 1%~60%, 1%~50%, 1%~40%, 1%~30%, 1%~20% It may remain in areas of 1%~10%, 10%~99%, 10%~90%, 10%~80%, 10%~70%, 10%~60%, 10%~50%, 10%~40%, 10%~30%, 10%~20%, 30%~99%, 30%~90%, 30%~80%, 30%~70%, 30%~60%, 30%~50%, 30%~40%, 50%~99%, 50%~90%, 50%~80%, 50%~70%, 50%~60%, 80%~99%, 80%~90%, or 90%~99%.

[0097] As shown in Figure 2, the electron transport layer residue 132 does not have a constant thickness, and the hole transport layer residue 152 may also be formed locally.

[0098] In one embodiment, the Hall transmission layer residue 152 may be formed by laser patterning, mechanical scribing, or both.

[0099] The aforementioned Hole transfer layer residue 152 has the advantage of strengthening the adhesion strength between the second electrode and the first electrode. Normally, when a thin film of a metal electrode (such as an Au or Ag thin film) is deposited onto a transparent electrode (the first electrode), the adhesion strength is poor due to the difference in crystal structure and surface energy between the two thin films. Therefore, a method of forming a seed layer of Ti, Ni, or Cr is used to improve the adhesion strength. The Hole transfer layer residue 152 has higher adhesion strength compared to the metal / transparent electrode, and when the Hole transfer layer residue remains partially, the surface area increases, resulting in higher adhesion strength. If the adhesion strength is not good, there is a very high possibility that problems will arise in the long-term reliability of large-scale photoelectric conversion semiconductor devices in the future.

[0100] In laser patterning, increasing the laser energy or the number of patterning passes may be necessary to completely remove residual material from the hole transmission layer, but this can cause laser damage to other multilayer thin films. Similarly, in mechanical patterning scribing, increasing the pressing force or the number of etching passes during mechanical etching may be necessary to completely remove residual material from the hole transmission layer, but this can cause damage to the transparent electrodes and glass substrates. Therefore, by avoiding excessive etching processes, the process can be simplified without damaging the multilayer thin films.

[0101] The second pitch is formed to allow current to flow between the perovskite light-absorbing semiconductor layers 140 of the separated cells, thereby forming positive and negative charges at opposite ends within the perovskite light-absorbing semiconductor layer 140.

[0102] More specifically, a positive charge is formed at the interface between the perovskite light-absorbing semiconductor layer 140 and the second electrode 160, and a negative charge is formed at the interface between the perovskite light-absorbing semiconductor layer 140 and the first electrode 120.

[0103] Furthermore, the separated cells, connected from the positive charge formation area of ​​the perovskite light-absorbing semiconductor layer 140 in one cell to the negative charge formation area of ​​the perovskite light-absorbing semiconductor layer 140 in the adjacent cell, can be connected in series as a whole.

[0104] According to one embodiment of the present invention, the hole transfer layer 150, the perovskite light-absorbing semiconductor layer 140, the electron transfer layer 130, and the second electrode 160 have a third pitch P3 formed on them.

[0105] The third pitch serves to divide the photoelectric conversion module of the present invention, which is formed in a monolithic pattern structure, into cells. [Embodiment]

[0106] First, a glass substrate was prepared and ITO was deposited on the substrate as the first electrode. Next, the first electrode was P1 patterned using a laser patterning method, and a SnO2 layer was formed as an electron transport layer covering the first electrode. Next, FAPbI3 was coated on the electron transport layer as a perovskite light-absorbing semiconductor layer, and NiO was formed on the perovskite light-absorbing semiconductor layer as a hole transport layer. Then, the electron transport layer, perovskite light-absorbing semiconductor layer, and hole transport layer were P2 patterned. Next, Au was deposited on the hole transport layer as the second electrode. Finally, the electron transport layer, perovskite light-absorbing semiconductor layer, hole transport layer, and the second electrode were P3 patterned to fabricate a perovskite photoelectric conversion semiconductor device. It was confirmed that the fabricated device operated with 0.5 nm of the electron transport layer remaining on the electrode.

[0107] Figure 4 is a cross-sectional view of a contact resistance measurement sample of Au / SnO2 / ITO according to an embodiment of the present invention.

[0108] To analyze the principle of how the device operates when an electron transport layer remains on the electrode in the P2 region, a sample was fabricated with the structure shown in Figure 4. In Figure 4, after forming SnO2 electron transport layers with thicknesses of 0 nm, 0.1 nm, 0.5 nm, 1 nm, 2 nm, 5 nm, 10 nm, and 20 nm, the current-voltage was measured by bringing the ends of the Au electrode into contact with the layer.

[0109] Figure 5 is a graph showing the current-voltage measurement curve for evaluating the contact resistance of Au / SnO2 / ITO according to an embodiment of the present invention.

[0110] As shown in Figure 5, similar current-voltage curves were observed when no SnO2 was formed (0 nm) and when approximately 0.1 nm of SnO2 was formed, indicating that similar contact resistance values ​​were present. Furthermore, when SnO2 was formed to a thickness of 0.1 nm to 2 nm, the contact resistance value increased slightly as the SnO2 thickness increased, but a linear current-voltage curve was observed, indicating that Au / SnO2 / ITO still exhibited ohmic contact. However, when the SnO2 thickness was 5 nm or more, the current-voltage curve did not appear linear, indicating rectifying or Schottky contact, which was observed to result in a rapid increase in contact resistance. Therefore, it was concluded that the appropriate remaining SnO2 thickness is 2 nm or less.

[0111] As described above, although the embodiments have been explained based on limited drawings, a person with ordinary skill in the art can apply various technical modifications and variations based on the foregoing. For example, the described techniques may be performed in a different order than described, and / or the described systems, structures, devices, circuits, and other components may be combined or assembled in a different manner than described, or substituted or replaced by other components or equivalents, and still achieve the desired results.

[0112] Therefore, other realizations, other embodiments, and those equivalent to the claims described below also fall within the scope of the claims. [Explanation of Symbols]

[0113] 110: Circuit board 120: 1st electrode 130: Electron transport layer 132: Electron transport layer residue 140: Perovskite light-absorbing semiconductor layer 150: Hole layer 152: Hall transmission layer residue 160: 2nd electrode

Claims

1. circuit board and A first electrode formed on the substrate, An electron transport layer formed on the first electrode, A perovskite light-absorbing semiconductor layer formed on the electron transport layer, A hole transfer layer formed on the perovskite light-absorbing semiconductor layer, A second electrode formed on the aforementioned Hall transmission layer, Includes, The first electrode has a first pitch formed therein. The electron transport layer, the perovskite light-absorbing semiconductor layer, and the hole transport layer have a second pitch formed thereon. The electron transport layer is a perovskite photoelectric semiconductor element that includes electron transport layer residue at the second pitch.

2. circuit board and A first electrode formed on the substrate, A hole transmission layer formed on the first electrode, A perovskite light-absorbing semiconductor layer formed on the aforementioned hole transfer layer, An electron transport layer formed on the perovskite light-absorbing semiconductor layer, A second electrode formed on the electron transport layer, Includes, The first electrode has a first pitch formed therein. The hole transfer layer, the perovskite light-absorbing semiconductor layer, and the electron transfer layer have a second pitch formed thereon. The Hole transfer layer is a perovskite photoelectric conversion semiconductor element that includes Hole transfer layer residue at the second pitch.

3. The perovskite photoelectric conversion semiconductor element according to claim 1 or 2, wherein the electron transport layer residue or the hole transport layer residue has a thickness range of 0.1 nm to 2 nm.

4. The perovskite photoelectric semiconductor element according to claim 1 or 2, wherein the electron transport layer residue or the hole transport layer residue is included on the first electrode of the second pitch in an area of ​​0.05% to 99%.

5. The perovskite photoelectric semiconductor element according to claim 1 or 2, wherein the electron transport layer residue or the hole transport layer residue is formed locally.

6. The perovskite photoelectric semiconductor element according to claim 1 or 2, wherein the electron transport layer residue or the hole transport layer residue is formed by laser patterning, mechanical scribing, or both.

7. The perovskite photoelectric conversion semiconductor element according to claim 1 or 2, wherein the electron transfer layer or the hole transfer layer is formed to cover at least a portion of the first electrode and the substrate.

8. The perovskite photoelectric conversion semiconductor element according to claim 1 or 2, wherein the second electrode is formed to cover at least a portion of the first electrode, the electron transfer layer, the perovskite light absorption semiconductor layer, and the hole transfer layer.

9. The perovskite photoelectric conversion semiconductor element according to claim 1 or 2, wherein the electron transport layer, the hole transport layer, the perovskite light absorption semiconductor layer, and the second electrode have a third pitch formed on them.

10. The first electrode, the second electrode, or both thereof, are transparent electrodes or metal electrodes. The transparent electrode is made of ITO, FTO, and SnO. ２ It comprises one or more selected from the group consisting of Al:ZnO, B:ZnO, graphene, PEDOT:PSS, Ag nanowires, graphene, and carbon nanotubes. The perovskite photoelectric conversion semiconductor element according to claim 1 or 2, wherein the metal electrode comprises one or more selected from the group consisting of Au, Ag, Ni, Cu, Mo, Pt, W, Al and its alloys.

11. The electron transport layer is TiO ２ , SnO ２ WS ２ , WSe ２ ZnO and C ６０ A perovskite photoelectric conversion semiconductor element according to claim 1 or 2, further comprising one or more selected from the group consisting of the following.

12. The aforementioned hole transfer layer is NiO ｘ , Spiro-OMeTAD, PTAA, P ３ A perovskite photoelectric conversion semiconductor device according to claim 1 or 2, further comprising one or more selected from the group consisting of HT, PEDOT:PSS, and self-assembled monolayer.

13. The perovskite light-absorbing semiconductor layer contains an ABX ３ compound having a structure, The above A is one or more selected from the group consisting of methylammonium, formamidinium, Cs, and Rb. The aforementioned B is one or more selected from the group consisting of Pb, Sn, Ge, Sb, and Bi. The perovskite photoelectric conversion semiconductor element according to claim 1 or 2, wherein X is one or more selected from the group consisting of I, Br, and Cl.

14. The perovskite photoelectric conversion semiconductor element is a large-scale photoelectric conversion module, wherein several cells are connected in series in a monolithic structure and energized, as described in claim 1 or 2.

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