Copper indium gallium selenide PN junction and its preparation method and application in semiconductor thin film components and photoelectric sensing modules

Abstract

This application relates to a PN junction, its preparation method and uses, a semiconductor thin film component (especially a photodiode component) comprising the PN junction, a photoelectric sensing module comprising the semiconductor thin film component, and their extensive uses. The PN junction comprises a P-type copper indium gallium selenide semiconductor thin film layer and an N-type copper indium gallium selenide semiconductor thin film layer. The N-type copper indium gallium selenide semiconductor thin film layer is composed of elements such as copper, indium and gallium, wherein the molar ratio of copper to indium is in the range of 1.1 to 1.5 and has the chemical formula Cu(In x Ga 1‑x )Se2, where the value of x is in the range of 0.6 to 0.9. The method for preparing the PN junction uses a quaternary target, is a dry process, does not require a selenization treatment, and can fabricate the PN junction on a flexible substrate.

Description

Technical Field

[0001] The present application relates to a PN junction, a preparation method and use thereof, a semiconductor thin film component (especially a photodiode component) comprising the PN junction, and a photoelectric sensing module comprising the semiconductor thin film component and a wide range of uses thereof. Background Art

[0002] Copper Indium Gallium Selenide semiconductor film not only has excellent photosensitivity to visible light, but also has better photosensitivity to light in the infrared to near-infrared range (780 to 1100nm) compared to general semiconductor film materials. Therefore, copper indium gallium selenide semiconductor film can be used to manufacture wide-band photodiode components.

[0003] The conventional copper indium gallium selenide photodiode assembly comprises (1) a metal electrode thin film layer as an anode, (2) a P-type copper indium gallium selenide semiconductor thin film layer as a light absorbing layer, (3) an N-type compound semiconductor thin film layer as a buffer layer, (4) a transparent metal oxide conductive thin film layer as a conductive layer, and (5) a transparent metal oxide thin film layer as a cathode. Figure 1 ).

[0004] The metal electrode thin film layer used as the anode is usually prepared by sputtering using molybdenum metal.

[0005] As a light-absorbing layer, the P-type copper indium gallium selenide semiconductor thin film layer with high photoelectric conversion characteristics is often deposited on a substrate coated with a metal anode thin film layer by vacuum magnetron sputtering, vacuum co-evaporation, printing or electroplating, using binary, ternary or quaternary compound targets selected from elements such as copper, indium, gallium and selenium, and then subjected to a selenization process. The selenization process is the most important process in the copper indium gallium selenide process. The purpose of the selenization process is to increase the proportion of selenium to increase the surface energy gap of the component, thereby solving the problem of low open circuit voltage. The selenization process also determines the grain size and composition distribution of copper indium gallium selenide, thereby affecting the photoelectric conversion efficiency of copper indium gallium selenide. The selenization process mainly converts metal precursors into selenide semiconductor materials in a chemical atmosphere of selenium. There are two common selenization processes, namely rapid thermal process (RTP) selenization and hydrogen selenide (H2Se) heat treatment. RTP heat treatment uses solid selenium source for heating, which has the advantage of fast production rate, but the disadvantage is that it is difficult to control the uniformity of the atmosphere, so the grain composition cannot be adjusted, resulting in low efficiency. H2Se heat treatment uses hydrogen selenide for selenization, which has the advantage of controlling the atmosphere to obtain high-efficiency components, but the disadvantage is that the batch tubular furnace reaction has a slow production rate, resulting in a long reaction time (8-10 hours).

[0006] The N-type compound semiconductor thin film layer as a buffer layer must match the energy gap of the light absorbing layer to form a depletion region of sufficient thickness. The buffer layer can prevent the light absorbing layer from being damaged by the high-energy sputtering coating process in the subsequent process and protect the crystal structure inside the light absorbing layer. The P-type copper indium gallium selenide semiconductor thin film layer has a direct energy gap, and the surface can be doped with gallium or sulfur ions to increase the energy gap. Cadmium sulfide (CdS) is often used as the material for the N-type compound semiconductor layer. However, based on environmental considerations, a semiconductor thin film component with an N-type compound semiconductor layer that does not contain cadmium is needed.

[0007] CN 108470783 A discloses a photosensitive component, comprising a P-type copper indium gallium selenide semiconductor thin film layer, an intrinsic copper indium gallium selenide thin film layer and an N-type copper indium gallium selenide semiconductor thin film layer. The energy bandwidth of the intrinsic copper indium gallium selenide thin film is about Eg=1.37eV, and its chemical structure is β-Cu 0.49 (In 0.56 Ga 0.44 )3Se5. It can be seen that the film plating of intrinsic copper indium gallium selenide requires an excess of selenium elements, and can only be achieved by using a high-temperature selenization process. It cannot be achieved by simply using a sputtering or evaporation coating method. In the PIN photosensitive component, the production of the P-type copper indium gallium selenide semiconductor thin film layer is based on the contact with the copper or copper alloy electrode after the intrinsic copper indium gallium selenide thin film layer is plated, and the copper element of the electrode is diffused into the intrinsic copper indium gallium selenide thin film layer through high-temperature annealing. The diffusion depth of the copper element in this method is insufficient, resulting in a defective structure at the interface between the metal electrode and the P-type copper indium gallium selenide semiconductor thin film layer, and a good ohmic contact cannot be formed. Furthermore, CN 108470783A mentions that the intrinsic copper indium gallium selenide thin film layer is mainly used to absorb light, so that the received light forms electron-hole pairs, and then forms an electric current through the built-in electric field of the PIN structure to convert it into an electrical signal. However, the intrinsic copper indium gallium selenide thin film layer has a lot of crystal structure defects, and the patent records that the intrinsic copper indium gallium selenide thin film layer has a thickness range of 300 nanometers to 3,000 nanometers, and the P-type copper indium gallium selenide semiconductor thin film layer and the N-type copper indium gallium selenide semiconductor thin film layer are 50 nanometers to 300 nanometers, so there are many defective structures inside the intrinsic copper indium gallium selenide thin film layer. The defective structure will make the efficiency of electron-hole pair formation low, and the metal electrode and the P-type copper indium gallium selenide semiconductor thin film layer cannot form a good ohmic contact, so the built-in electric field cannot effectively separate the electron-hole pairs to form a carrier current, and the PIN copper indium gallium selenide component structure cannot operate effectively. In addition, since the intrinsic copper indium gallium selenide is thermodynamically unstable, it is easy to phase separate during annealing, so it is difficult to reduce structural defects by annealing.

[0008] The selenization process of the P-type CIGS semiconductor thin film layer and the plating of the N-type compound semiconductor layer using cadmium sulfide both involve high-temperature chemical reactions, which affect the internal structure of the thin film, thereby damaging the photoelectric conversion efficiency of the resulting photodiode component. Therefore, the technical field needs a PN junction that does not require selenization treatment and does not contain cadmium, and the PN junction is suitable for use in semiconductor thin film components. Summary of the invention

[0009] An object of the present invention is to provide a PN junction that does not require selenization and uses a cadmium-free buffer layer.

[0010] Another object of the present invention is to provide a semiconductor thin film component, especially a semiconductor photodiode component, comprising the PN junction. According to one embodiment of the present invention, the semiconductor thin film photodiode component further comprises a layer containing a molybdenum metal compound. According to another embodiment of the present invention, the semiconductor thin film photodiode component further comprises a light conversion thin film layer that emits light having a wavelength of 350nm to 1300nm. According to yet another embodiment of the present invention, the semiconductor thin film photodiode component further comprises a layer containing a molybdenum metal compound and a light conversion thin film layer that emits light having a wavelength of 350nm to 1300nm.

[0011] Another object of the present invention is to provide a photoelectric sensing module, comprising a semiconductor thin film component having the above-mentioned PN junction, in particular a semiconductor thin film photodiode component.

[0012] Another object of the present invention is to provide a use of the photoelectric sensing module, which is used for biometric identification, infrared imaging night vision system sensing, near-infrared photoelectric switch or X-ray sensing.

[0013] Additional aspects and advantages of the embodiments of the present application will be described, shown, or explained in part in the subsequent description through implementation of the embodiments of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The following will briefly describe the drawings necessary for describing the embodiments of the present application or the prior art to facilitate the description of the embodiments of the present application. Obviously, the drawings described below are only some of the embodiments in the present application. For those skilled in the art, without the need for creative work, drawings of other embodiments can still be obtained based on the structures illustrated in these drawings.

[0015] Figure 1 The present invention is a photodiode component structure including a P-type copper indium gallium selenide semiconductor thin film layer in the prior art.

[0016] Figure 2 It is a PN junction according to the present invention.

[0017] Figure 3 The semiconductor thin film photodiode component according to the present invention.

[0018] Figure 4 One aspect of a semiconductor thin film photodiode device according to the present invention comprises a layer containing a molybdenum metal compound.

[0019] Figure 5 One aspect of the semiconductor thin film photodiode device according to the present invention comprises a light conversion thin film layer.

[0020] Figure 6 This is one aspect of a semiconductor thin film photodiode component according to the present invention, which includes a layer containing a molybdenum metal compound and a light conversion thin film layer.

[0021] Figure 7 The examples are used to illustrate the characteristic curves of current density and voltage when the photodiode components of the present invention and the comparative example are applied to solar cells. DETAILED DESCRIPTION

[0022] The embodiments of the present application will be described in detail below. In the full text of the present application specification, the same or similar components and components with the same or similar functions are represented by similar reference numerals. The embodiments of the accompanying drawings described herein are illustrative and graphical and are used to provide a basic understanding of the present application. The embodiments of the present application should not be interpreted as limiting the present application.

[0023] To facilitate understanding of the disclosure set forth herein, several terms are defined below.

[0024] The term "about" means an acceptable error for the particular value as determined by one of ordinary skill in the art, depending on how the value is measured or determined.

[0025] In this document, unless otherwise specified, the singular forms "a", "an" and "the" also include the plural forms. Any and all embodiments and exemplary terms ("for example" and "such as") herein are intended only to highlight the present invention and are not intended to limit the scope of the present invention. The terms in this specification should not be considered to imply that any unrequested methods and conditions may constitute necessary features for implementing the present invention.

[0026] In the detailed description and claims, a list of items connected by the terms "one of," "one of," "a kind of," or other similar terms may mean any of the listed items. For example, if items A and B are listed, the phrase "one of A and B" means only A or only B. In another example, if items A, B, and C are listed, the phrase "one of A, B, and C" means only A; only B; or only C. Item A may include a single component or multiple components. Item B may include a single component or multiple components. Item C may include a single component or multiple components.

[0027] In the detailed description and claims, a list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may include a single component or multiple components. Item B may include a single component or multiple components. Item C may include a single component or multiple components.

[0028] The present invention will be described in detail below.

[0029] [PN interface]

[0030] The PN junction of the present invention comprises the following semiconductor thin film layers:

[0031] (a) a P-type copper indium gallium selenide semiconductor thin film layer; and

[0032] (b) N-type copper indium gallium selenide semiconductor thin film layer.

[0033] The PN junction ( Figure 2 ) By replacing the conventional N-type compound semiconductor thin film layer with an N-type copper indium gallium selenide semiconductor thin film layer, the purpose of reducing the selenization process and lowering the process temperature is achieved.

[0034] aP type copper indium gallium selenide semiconductor thin film layer

[0035] The molar ratio of copper to indium in the P-type copper indium gallium selenide semiconductor material of the P-type copper indium gallium selenide semiconductor thin film layer used in the present invention is in the range of 1.6 to 2, for example, 1.60, 1.65, 1.70, 1.75, 1.80, 1.85, 1.90, 1.95 or 2, preferably 1.65 to 1.90, more preferably 1.75 to 1.80. When the molar ratio is higher than 2, the crystal structure inside the film layer will form too much CuIn Acceptor defects affect light absorption efficiency and hole carrier transport capacity; when the mole ratio is lower than 1.6, P-type copper indium gallium selenide semiconductor cannot be produced. P-type copper indium gallium selenide semiconductor using the mole ratio has lower crystal structure defects, higher light absorption coefficient and hole carrier transport capacity.

[0036] According to one aspect of the present invention, the P-type copper indium gallium selenide semiconductor material has a chemical formula of Cu(In x Ga 1-x )Se2, wherein 0.5≤x≤0.625, preferably 0.52≤x≤0.62. For example, but not limited to, 0.5, 0.501, 0.503, 0.505, 0.507, 0.509, 0.511, 0.513, 0.515, 0.517, 0.519, 0.521, 0.523, 0.525, 0.527, 0.529, 0.531, 0.533, 0.535, 0.537, 0.539, 0.541, 0.543, 0.545, 0.547, 0.549, 0.551, 0.553, 0.555, 0.557, 0.559, 0.56 1. 0.563, 0.565, 0.567, 0.569, 0.571, 0.573, 0.575, 0.577, 0.579, 0.581, 0.583, 0.585, 0.587, 0.589, 0.591, 0.593, 0.595, 0.597, 0.599, 0.601, 0.603, 0.605, 0.607, 0.609, 0.611, 0.613, 0.615, 0.617, 0.619, 0.621, 0.623, or 0.625.

[0037] bN-type copper indium gallium selenide semiconductor thin film layer

[0038] The molar ratio of copper to indium in the N-type copper indium gallium selenide semiconductor of the N-type copper indium gallium selenide semiconductor thin film layer used in the present invention is in the range of 1.1 to 1.5, for example, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45 or 1.5, preferably 1.1 to 1.35, more preferably 1.2 to 1.25. When the molar ratio is higher than 1.5, the N-type copper indium gallium selenide semiconductor cannot be produced. When the molar ratio is lower than 1.1, the In indium in the crystal structure of the film layer is Cu There will be too many donor defects, which will affect the electron carrier transmission capacity. The N-type copper indium gallium selenide semiconductor using the mole ratio does not require selenization treatment.

[0039] According to one aspect of the present invention, the N-type copper indium gallium selenide semiconductor material has a chemical formula of Cu(In x Ga1-x )Se2, wherein 0.63≤x≤0.9, preferably 0.7≤x≤0.8. For example but not limited to 0.63, 0.631, 0.633, 0.635, 0.637, 0.639, 0.641, 0.643, 0.645, 0.647, 0.649, 0.651, 0.653, 0.655, 0.657, 0.659, 0.661, 0.663, 0.665, 0.667, 0.669, 0.671, 0.673, 0.675, 0.677, 0.679, 0.681, 0.683, 0.685, 0.687, 0.689, 0.691, 0.693, 0.6 95, 0.697, 0.699, 0.701, 0.703, 0.705, 0.707, 0.709, 0.711, 0.713, 0.715, 0.717, 0.719, 0.721, 0.723, 0.725, 0.727, 0.729, 0.731, 0.733, 0.735, 0.737, 0.739, 0.741, 0.743, 0.745, 0.747, 0.749, 0.751, 0.753, 0.755, 0.757, 0.759, 0.761, 0.763 , 0.765, 0.767, 0.769, 0.771, 0.773, 0.775, 0.777, 0.779, 0.781, 0.783, 0.785, 0.787, 0.789, 0.791, 0.793, 0.795, 0.797, 0.799, 0.801, 0.803, 0.805, 0.807, 0.809, 0.811, 0.813, 0.815, 0.817, 0.819, 0.821, 0.823, 0.825, 0.827, 0.829, 0.831, 0 .833, 0.835, 0.837, 0.839, 0.841, 0.843, 0.845, 0.847, 0.849, 0.851, 0.853, 0.855, 0.857, 0.859, 0.861, 0.863, 0.865, 0.867, 0.869, 0.871, 0.873, 0.875, 0.877, 0.879, 0.881, 0.883, 0.885, 0.887, 0.889, 0.891, 0.893, 0.895, 0.897, 0.899, or 0.9.

[0040] The PN junction according to the present invention can be used in semiconductor thin film devices, such as but not limited to semiconductor transistor devices or semiconductor photodiode devices, especially semiconductor photodiode devices.

[0041] [Semiconductor thin film photodiode components]

[0042] The semiconductor thin film photodiode assembly of the present invention comprises the following parts ( Figure 3 ):

[0043] (a) a metal electrode thin film layer serving as an anode;

[0044] (b) a PN junction according to the present invention;

[0045] (c) a transparent metal oxide conductive thin film layer as a conductive layer; and

[0046] (d) Transparent metal oxide thin film layer as cathode.

[0047] The semiconductor thin film photodiode component does not require selenization treatment and does not involve an N-type compound semiconductor layer of cadmium sulfide during the preparation process, so it does not involve high-temperature chemical reactions and can be treated at a temperature of about 150°C to 450°C to avoid affecting the internal structure of the film. Compared with traditional photodiode components, it has higher photoelectric conversion efficiency.

[0048] a. Metal electrode thin film layer as anode

[0049] The metal anode film layer is not particularly limited and can be any metal electrode material known to those having ordinary knowledge in the technical field to which the present invention belongs, such as but not limited to materials containing molybdenum (Mo), such as but not limited to Mo, Ti / Mo, Cr / Mo, Al / Mo, Au / Mo, or materials containing titanium, gold, silver, copper or chromium.

[0050] b.PN interface

[0051] The PN junction is a PN junction according to the present invention, comprising a P-type copper indium gallium selenide semiconductor thin film layer as a light absorbing layer and an N-type copper indium gallium selenide semiconductor thin film layer as a buffer layer. The P-type copper indium gallium selenide semiconductor thin film layer as a light absorbing layer has a photoelectric conversion capability and a high light absorption coefficient (greater than 105cm -1 ), can absorb light with a wavelength range of 350nm to 1300nm, preferably light with a wavelength range of 700nm to 1100nm, and more preferably light with a wavelength range of 780nm to 900nm. The N-type copper indium gallium selenide semiconductor thin film layer acts as a buffer layer, matches the energy gap of the light absorbing layer to form a depletion region of sufficient thickness, and prevents the light absorbing layer from being damaged by the high-energy sputtering coating process in the subsequent process, and protects the crystal structure inside the thin film.

[0052] c. Transparent metal oxide thin film layer as a conductive layer

[0053] The transparent metal oxide thin film layer used as a conductive layer is not particularly limited and can be any metal electrode and material known to those with ordinary knowledge in the technical field to which the present invention belongs, such as but not limited to i-ZnO / ITO, i-ZnO / AZO, i-ZnO / BZO (ZnO: B), i-ZnO / IWO (In2O3: W), i-ZnO / IWZO ​​(In2O3: W: ZnO).

[0054] d. Transparent metal oxide thin film layer as cathode

[0055] The transparent metal oxide thin film layer used as the cathode is not particularly limited and may be any metal electrode and material known to those having ordinary knowledge in the technical field to which the present invention belongs, such as but not limited to i-ZnO / ITO, i-ZnO / AZO, i-ZnO / BZO (ZnO:B), i-ZnO / IWO (In2O3:W), i-ZnO / IWZO ​​(In2O3:W:ZnO).

[0056] According to one aspect of the present invention, the semiconductor thin film photodiode device further comprises a layer containing a molybdenum metal compound as a hole transport thin film layer. The hole transport thin film layer is preferably located between the metal anode thin film layer and the P-type copper indium gallium selenide semiconductor thin film layer in the PN junction ( Figure 4 ), which is used to reduce the potential difference between the molybdenum metal film anode layer and the P-type copper indium gallium selenide semiconductor film layer, thereby improving the efficiency of hole transport to the anode. The hole transport film layer is a layer containing a molybdenum metal compound, and its material is, for example but not limited to, molybdenum dioxide (MoO2), molybdenum diselenide (MoSe2) or a molybdenum metal compound doped with at least one of trace elements such as lithium, sodium, potassium, rubidium, and cesium.

[0057] When manufacturing copper indium gallium selenide photodiodes, soda-lime glass substrates are often used because the alkali metal ions in the soda-lime glass substrate can diffuse into the inside of the copper indium gallium selenide semiconductor thin film layer under a high-temperature process, thereby improving the electrical properties of the semiconductor thin film layer. The hole transport thin film layer is suitable for the soda-lime glass substrate. On the other hand, when manufacturing thin film transistors, non-soda-lime glass substrates are often used to prevent the alkali metal ions in the soda-lime glass substrate from diffusing into the oxide layer inside the thin film transistor under a high-temperature process, thereby reducing the electrical properties of the thin film transistor. The hole transport thin film layer can be applied to a soda-lime glass substrate in the conventional sense, and when the hole transport thin film layer is applied to a non-soda-lime glass substrate, a high photoelectric conversion efficiency can also be maintained.

[0058] According to another aspect of the present invention, the semiconductor thin film photodiode component further comprises a light conversion thin film layer ( Figure 5). The light conversion film layer is mainly used to convert the absorbed incident light of different wavelengths into light that is easily absorbed by the P-type copper indium gallium selenide semiconductor thin film layer as a light absorption layer, such as light with a wavelength in the range of 350nm to 1300nm, preferably light in the range of 700 to 1100nm, and more preferably light with a wavelength of 780 to 900nm, thereby increasing the light absorption of the P-type copper indium gallium selenide thin film layer and promoting the photoelectric conversion effect of the photodiode component. The light conversion film layer also has the function of protecting the cathode / transparent conductive oxide film layer from chemical corrosion by water vapor and acid-base liquids, thereby increasing the life of the photodiode component. The material of the light conversion film layer is not particularly limited, and can be any luminescent material known to a person of ordinary skill in the technical field to which the present invention belongs, such as but not limited to a light emitting material selected from a group consisting of quantum dots, organic phosphorescent or fluorescent materials and rare earth materials.

[0059] According to another aspect of the present invention, the semiconductor thin film photodiode component also includes a layer containing a molybdenum metal compound as a hole transport thin film layer and a light conversion thin film layer ( Figure 6 ).

[0060] [Photoelectric sensing module]

[0061] The photoelectric sensing module of the present invention comprises a semiconductor thin film component having a PN junction according to the present invention.

[0062] According to one aspect of the present invention, the semiconductor thin film component is a semiconductor thin film photodiode component, and the photoelectric sensing module further includes a semiconductor thin film transistor component and a semiconductor light emitting component.

[0063] According to one aspect of the present invention, the semiconductor thin film photodiode component, the semiconductor thin film transistor component and the semiconductor light emitting component are integrated and manufactured on the same substrate.

[0064] According to one aspect of the present invention, the substrate is, for example but not limited to, a glass substrate or a stainless steel substrate, or a flexible substrate, for example but not limited to a plastic film substrate.

[0065] According to one aspect of the present invention, the material of the metal anode film layer in the semiconductor thin film photodiode component and the material of the source and drain electrodes in the semiconductor thin film transistor component are the same molybdenum metal compound and can be prepared simultaneously.

[0066] According to one aspect of the present invention, the semiconductor light emitting component may be, but is not limited to, an X-RAY, UV LED, IRLED, IR LD or RGB OLED light source.

[0067] The photoelectric sensing module according to the present invention can be used for biometric identification, infrared imaging night vision system sensing, near-infrared photoelectric switch or X-ray sensing.

[0068] [Method for preparing PN junction]

[0069] The present application provides a method for manufacturing the PN junction, which comprises the following steps:

[0070] (a) using a plurality of continuous vacuum magnetron sputtering coating chambers to coat a P-type copper indium gallium selenide semiconductor thin film layer and an N-type copper indium gallium selenide semiconductor thin film layer one by one using a target material containing one or more elements such as copper, indium, gallium and selenium; and

[0071] (b) annealing at a temperature in the range of 350° C. to 450° C. in an inert gas atmosphere,

[0072] The coating chamber described herein has two target positions.

[0073] The target material may be a binary, ternary or quaternary target material containing one or more of the elements copper, indium, gallium and selenium, preferably a ternary target material containing the elements copper, gallium and selenium, or a quaternary target material containing the elements copper, indium, gallium and selenium. For example, but not limited to, Cu y GaSe z , Cu y (In x Ga 1-x )Se z, wherein 0.5≤x≤0.9, for example but not limited to 0.5, 0.501, 0.503, 0.505, 0.507, 0.509, 0.511, 0.513, 0.515, 0.517, 0.519, 0.521, 0.523, 0.525, 0.527, 0.529, 0.531, 0.53 3. 0.535, 0.537, 0.539, 0.541, 0.543, 0.545, 0.547, 0.549, 0.551, 0.553, 0.555, 0.557, 0.559, 0.561, 0.563, 0.565, 0.567, 0.569, 0.571, 0.573, 0.5 75, 0.577, 0.579, 0.581, 0.583, 0.585, 0.587, 0.589, 0.591, 0.593, 0.595, 0.597, 0.599, 0.601, 0.603, 0.605, 0.607, 0.609, 0.611, 0.613, 0.615, 0 .617, 0.619, 0.621, 0.623, 0.625, 0.63, 0.631, 0.633, 0.635, 0.637, 0.639, 0.641, 0.643, 0.645, 0.647, 0.649, 0.651, 0.653, 0.655, 0.657, 0.659, 0 .661, 0.663, 0.665, 0.667, 0.669, 0.671, 0.673, 0.675, 0.677, 0.679, 0.681, 0.683, 0.685, 0.687, 0.689, 0.691, 0.693, 0.695, 0.697, 0.699, 0.701 , 0.703, 0.705, 0.707, 0.709, 0.711, 0.713, 0.715, 0.717, 0.719, 0.721, 0.723, 0.725, 0.727, 0.729, 0.731, 0.733, 0.735, 0.737, 0.739, 0.741, 0.74 3. 0.745, 0.747, 0.749, 0.751, 0.753, 0.755, 0.757, 0.759, 0.761, 0.763, 0.765, 0.767, 0.769, 0.771, 0.773, 0.775, 0.777, 0.779, 0.781, 0.783, 0.7 85, 0.787, 0.789, 0.791, 0.793, 0.795, 0.797, 0.799, 0.801, 0.803, 0.805, 0.807, 0.809, 0.811, 0.813, 0.815, 0.817, 0.819, 0.821, 0.823, 0.825, 0.827, 0.829, 0.831, 0.833, 0.835, 0.837, 0.839, 0.841, 0.843, 0.845, 0.847, 0.849, 0.851, 0.853, 0.855, 0.857, 0.859, 0.861, 0.863, 0.865, 0.867, 0.869, 0.871, 0.873, 0.875, 0.877, 0.879, 0.881, 0.883, 0.885, 0.887, 0.889, 0.891, 0.893, 0.895, 0.897, 0.899 or 0.9;.

[0074] wherein 0.8≤y≤1.2, for example but not limited to 0.80, 0.801, 0.803, 0.805, 0.807, 0.809, 0.811, 0.813, 0.815, 0.817, 0.819, 0.821, 0.823, 0.825, 0.827, 0.829, 0.831, 0.833, 0.835, 0.837, 0.839, 0.841, 0.843, 0.845, 0.847, 0.849, 0.851, 0.853, 0.855, 0.857, 0.859, 0.861, 0.863, 0.865, 0.867, 0.869, 0.871, 0.873, 0.8 75, 0.877, 0.879, 0.881, 0.883, 0.885, 0.887, 0.889, 0.891, 0.893, 0.895, 0.897, 0.899, 0.901, 0.903, 0.905, 0.907, 0.909, 0.911, 0.913, 0.915, 0. 917, 0.919, 0.921, 0.923, 0.925, 0.927, 0.929, 0.931, 0.933, 0.935, 0.937, 0.939, 0.941, 0.943, 0.945, 0.947, 0.949, 0.951, 0.953, 0.955, 0.957, 0 .959, 0.961, 0.963, 0.965, 0.967, 0.969, 0.971, 0.973, 0.975, 0.977, 0.979, 0.981, 0.983, 0.985, 0.987, 0.989, 0.991, 0.993, 0.995, 0.997, 0.999 , 1.001, 1.003, 1.005, 1.007, 1.009, 1.011, 1.013, 1.015, 1.017, 1.019, 1.021, 1.023, 1.025, 1.027, 1.029, 1.031, 1.033, 1.035, 1.037, 1.039, 1.04 1, 1.043, 1.045, 1.047, 1.049, 1.051, 1.053, 1.055, 1.057, 1.059, 1.061, 1.063, 1.065, 1.067, 1.069, 1.071, 1.073, 1.075, 1.077, 1.079, 1.081, 1.0 83, 1.085, 1.087, 1.089, 1.091, 1.093, 1.095, 1.097, 1.099, 1.101, 1.103, 1.105, 1.107, 1.109, 1.111, 1.113, 1.115, 1.117, 1.119, 1.121, 1.123, 1.1.125, 1.127, 1.129, 1.131, 1.133, 1.135, 1.137, 1.139, 1.141, 1.143, 1.145, 1.147, 1.149, 1.151, 1.153, 1.155, 1.157, 1.159, 1.161, 1.163, 1.165, 1.167, 1.169, 1.171, 1.173, 1.175, 1.177, 1.179, 1.181, 1.183, 1.185, 1.187, 1.189, 1.191, 1.193, 1.195, 1.197, 1.199 or 1.2; and.

[0075] Where 1.8≤z≤2.2, for example but not limited to 1.8, 1.801, 1.803, 1.805, 1.807, 1.809, 1.811, 1.813, 1.815, 1.817, 1.819, 1.821, 1.823, 1.825, 1.827, 1.829, 1.831, 1.833, 1.835, 1.837, 1.839, 1.841, 1.843, 1.845, 1.847, 1.849, 1.851, 1.853, 1.855, 1.857, 1.859, 1.861, 1.863, 1.865, 1.867, 1.869, 1.871, 1.873, 1.875 , 1.877, 1.879, 1.881, 1.883, 1.885, 1.887, 1.889, 1.891, 1.893, 1.895, 1.897, 1.899, 1.901, 1.903, 1.905, 1.907, 1.909, 1.911, 1.913, 1.915, 1.9 17, 1.919, 1.921, 1.923, 1.925, 1.927, 1.929, 1.931, 1.933, 1.935, 1.937, 1.939, 1.941, 1.943, 1.945, 1.947, 1.949, 1.951, 1.953, 1.955, 1.957, 1. 959, 1.961, 1.963, 1.965, 1.967, 1.969, 1.971, 1.973, 1.975, 1.977, 1.979, 1.981, 1.983, 1.985, 1.987, 1.989, 1.991, 1.993, 1.995, 1.997, 1.999, 2.001, 2.003, 2.005, 2.007, 2.009, 2.011, 2.013, 2.015, 2.017, 2.019, 2.021, 2.023, 2.025, 2.027, 2.029, 2.031, 2.033, 2.035, 2.037, 2.039, 2.041 , 2.043, 2.045, 2.047, 2.049, 2.051, 2.053, 2.055, 2.057, 2.059, 2.061, 2.063, 2.065, 2.067, 2.069, 2.071, 2.073, 2.075, 2.077, 2.079, 2.081, 2.0 83, 2.085, 2.087, 2.089, 2.091, 2.093, 2.095, 2.097, 2.099, 2.101, 2.103, 2.105, 2.107, 2.109, 2.111, 2.113, 2.115, 2.117, 2.119, 2.121, 2.123, 2.2.125, 2.127, 2.129, 2.131, 2.133, 2.135, 2.137, 2.139, 2.141, 2.143, 2.145, 2.147, 2.149, 2.151, 2.153, 2.155, 2.157, 2.159, 2.161, 2.163, 2.165, 2.167, 2.169, 2.171, 2.173, 2.175, 2.177, 2.179, 2.181, 2.183, 2.185, 2.187, 2.189, 2.191, 2.193, 2.195, 2.197, 2.199 or 2.2.

[0076] The annealing process uses a green laser or an electric heater as a heating source and the process is a completely dry process without selenization treatment.

[0077] The inert gas is not particularly limited, and can be any inert gas known to those skilled in the art, such as but not limited to nitrogen and argon.

[0078] The rapid annealing is not selenization and does not involve selenium-containing substances. The heating source used is, for example, but not limited to, a green laser or an electric heater.

[0079] According to one aspect of the present invention, when a green laser is used as a heating source, the annealing time ranges from 10 to 120 seconds. According to another aspect of the present invention, when an electric heater is used as a heating source, the annealing time ranges from 180 to 600 seconds.

[0080] According to one aspect of the present invention, the PN junction is manufactured on a flexible substrate.

[0081] [Method for preparing semiconductor thin film photodiode assembly]

[0082] The semiconductor thin film photodiode component is prepared by vacuum magnetron sputtering coating. When a light conversion thin film layer exists, the light conversion thin film layer is prepared by spray coating, screen printing coating, spin coating, slit coating, thermal transfer coating or transfer film.

[0083] Because the temperature is controlled within 450℃ and no selenization process is required, during the production process of the photodiode component, there will be no chemical reaction or thermal aging on the thin film layer structure or internal metal circuit of the thin film transistor component that has been produced on the substrate, which will cause the two components to lose their function when integrated on the same substrate. This can reduce the number of steps in the production process and ensure the working ability of the components after the two components are integrated.

[0084] Preparation Example

[0085] Preparation of PN interface

[0086] 1. Place the substrate in a vacuum coating chamber for coating a P-type copper indium gallium selenide semiconductor thin film layer. The chamber has two target positions, which use a quaternary target material (Cu(In 0.63 Ga 0.27 )Se2). The film is deposited by co-sputtering at a coating rate of 0.1 micrometer to 0.2 micrometer per minute. The thickness of the obtained P-type copper indium gallium selenide semiconductor film layer is in the range of 1 micrometer to 2 micrometers;

[0087] 2. The substrate obtained in step 1 is transferred to a vacuum coating chamber for coating an N-type copper indium gallium selenide semiconductor thin film layer. The chamber has two target positions, one of which uses a ternary target containing atoms of copper, gallium and selenium (no In, CuGaSe2), and the other uses a quaternary target containing atoms of copper, indium, gallium and selenium (Cu(In 0.63 Ga 0.27 )Se2). The film is deposited by co-sputtering at a film deposition rate of 0.01 micrometer to 0.02 micrometer per minute. The thickness of the obtained N-type copper indium gallium selenide semiconductor film layer is in the range of 0.05 micrometer to 0.1 micrometer.

[0088] Preparation of a semiconductor thin film photodiode component comprising the PN junction

[0089] 1. Place the glass substrate in a vacuum coating chamber for coating molybdenum metal film, heat it to 250 degrees, and then use magnetron sputtering to coat a 0.8 micron thick molybdenum (Mo) metal film layer as the metal electrode film layer of the anode; the pressure in the chamber during coating is between 1.0 and 5.0 x 10 -3 mbar range;

[0090] 2. The substrate coated with the molybdenum metal anode film obtained in step 1 is transferred to a vacuum coating chamber for coating sodium molybdenum (Mo:Na) to coat a sodium molybdenum film with a thickness of 0.01 μm to 0.03 μm as a hole transport film layer, wherein sodium accounts for 12% of the total weight of the sodium molybdenum metal compound target used;

[0091] 3. Prepare a PN junction using the substrate obtained in step 2 by using the steps for preparing a PN junction;

[0092] 4. The substrate obtained in step 3 is transferred to a vacuum chamber for rapid annealing, and annealed at a temperature in the range of 350° C. to 450° C. in an inert gas atmosphere for a time in the range of 100 to 300 seconds;

[0093] 5. The substrate obtained in step 4 is transferred to a vacuum coating chamber for coating a transparent metal oxide thin film layer as a cathode. The chamber has two target positions. First, an intrinsic zinc oxide thin film with a thickness of about 0.01 μm to 0.02 μm is coated on the N-type copper indium gallium selenide semiconductor thin film layer after rapid annealing. Then, an indium tin oxide thin film with a thickness of about 0.01 μm to 0.02 μm is coated on the intrinsic zinc oxide thin film.

[0094] A semiconductor thin film photodiode assembly comprising glass substrate / Mo (0.8 micron) / Mo:Na (0.03 micron) / P-type copper indium gallium selenide (2 micron) / N-type copper indium gallium selenide (0.05 micron) / i-ZnO (0.01 micron) / ITO (0.02 micron) was obtained. When the photodiode assembly is applied to a solar cell, the characteristic curve of the current density and voltage is shown in Figure 7 , where the short-circuit current (J sc ) is 32.716 mA / cm 2 , open circuit voltage (V oc ) is 649mV, the fill factor (FF) is 75.5% and the power generation efficiency (EFF) is 16.03%.

[0095] Examples and Comparative Examples

[0096] Table 1 provides a comparison between the embodiments of the photodiode assembly of the present application and the comparative examples recorded in the literature.

[0097]

[0098] Table 1

[0099] Comparative Example 1: Inline Cu(In,Ga)Se2 Co-evaporation for High-Efficiency SolarCells and Modules (IEEE JOURNAL OF PHOTOVOLTAICS, VOL.3, NO.3, PAGE 1100-1105, JULY 2013).

[0100] Comparative Example 2: Surface modification of CIGS film by annealing and its effect on the band structure and photovoltaic properties of CIGS solar cells (CURRENTAPPLIED PHYSICS, 15 (2015) 18-24).

[0101] Comparative Example 3: Study of thin film solar cells in high temperature condition (ENERGY PROCEDIA 74 (2015) 1410–1417).

[0102] Comparative Example 4: Deposition Technologies of High-Efficiency CIGS Solar Cells: Development of Two-Step and Co-Evaporation Processes (CRYSTALS2018,8,296).

[0103] Comparative Example 1 is about soda-lime glasses / Mo (about 0.35±0.02 microns) / Copper indium gallium selenide (1.7±0.3 microns) / Cadmium sulfide (0.05 microns) / Intrinsic zinc oxide (i-ZnO, 0.09±0.01 microns) / ZnO:Al (0.35±0.02 microns) / Magnesium fluoride MgF2 (0.105±0.005 microns)

[0104] Comparative Example 2 is about soda-lime glasses / Mo / Copper indium gallium selenide (2.0 microns) / Cadmium sulfide (0.05 microns) / Intrinsic zinc oxide (i-ZnO, 0.05 microns) / ZnO:Al (0.35 microns)

[0105] Comparative Example 3 is about soda-lime glasses / Mo / Copper Indium Gallium Selenide (3.0 microns) / Cadmium Sulfide (0.05 microns) / ZnO (0.2 microns)

[0106] Comparative Example 4 is about soda-lime glasses / Mo (about 1.0 micron) / Copper indium gallium selenide (about 2.3 micron) / Cadmium sulfide (about 0.05 micron) / Intrinsic zinc oxide (i-ZnO, about 0.08 micron) / ZnO:Al (0.35 micron)

[0107] Comparative Examples 1 to 4 all involve N-type semiconductor thin film layers containing cadmium sulfide. It is noteworthy that the photodiode device according to the present invention is prepared using a completely dry process that does not require selenization treatment, is environmentally friendly and does not contain cadmium. Under this condition, its power generation efficiency (16.03%) is reduced by at most 2.77% compared to the prior art (15.72% to 18.8%), and can even be increased by 0.31% compared to Comparative Example 2.

[0108] References throughout the specification to "some embodiments", "partial embodiments", "one embodiment", "another example", "example", "specific example" or "partial example" mean that at least one embodiment or example in the present application includes the specific features, structures, materials or characteristics described in the embodiments or examples. Therefore, descriptions appearing in various places throughout the specification, such as: "in some embodiments", "in an embodiment", "in one embodiment", "in another example", "in an example", "in a specific example" or "example", do not necessarily refer to the same embodiment or example in the present application. In addition, the specific features, structures, materials or characteristics herein may be combined in one or more embodiments or examples in any suitable manner.

[0109] Although illustrative embodiments have been demonstrated and described, those skilled in the art should understand that the embodiments described are not to be construed as limitations on the present application, and that changes, substitutions and modifications may be made to the embodiments without departing from the spirit, principles and scope of the present application.

[0110] Instruction drawing components

[0111] 10 Photodiode component structure

[0112] 11 Anode-metal electrode film layer

[0113] 12 Light-absorbing layer-P-type CIGS semiconductor thin film layer

[0114] 13 Buffer layer-N-type compound semiconductor thin film layer

[0115] 14 Transparent metal oxide conductive film layer

[0116] 15 Cathode - Transparent Metal Oxide Thin Film Layer

[0117] 20 PN junction

[0118] 22 P-type CIGS semiconductor thin film layer

[0119] 28 N-type CIGS semiconductor thin film layer

[0120] 30. Semiconductor thin film photodiode components

[0121] 31 Anode-metal electrode film layer

[0122] 34 Transparent metal oxide conductive film layer

[0123] 35 Cathode - Transparent Metal Oxide Thin Film Layer

[0124] 40. Semiconductor thin film photodiode components

[0125] 41 Anode-metal electrode film layer

[0126] 44 Transparent metal oxide conductive film layer

[0127] 45 Cathode - Transparent Metal Oxide Thin Film Layer

[0128] 46 Hole transport thin film layer-Molybdenum metal compound thin film layer

[0129] 50 semiconductor thin film photodiode components

[0130] 51 Anode-metal electrode film layer

[0131] 54 Transparent metal oxide conductive film layer

[0132] 55 Cathode - Transparent Metal Oxide Thin Film Layer

[0133] 57 Light conversion film layer

[0134] 60 Semiconductor thin film photodiode components

[0135] 61 Anode-metal electrode film layer

[0136] 64 Transparent metal oxide conductive film layer

[0137] 65 Cathode - Transparent Metal Oxide Thin Film Layer

[0138] 66 Hole transport film layer-Molybdenum metal compound film layer

[0139] 67 Light conversion film layer

Claims

1. A PN junction, comprising a P-type copper indium gallium selenide semiconductor thin film layer and an N-type copper indium gallium selenide semiconductor thin film layer, wherein the atomic molar ratio of copper to indium in the P-type copper indium gallium selenide semiconductor thin film layer is in the range of 1.6 to 2; and wherein the atomic molar ratio of copper to indium in the N-type copper indium gallium selenide semiconductor thin film layer is in the range of 1.1 to 1.

5.

2. The PN junction according to claim 1, wherein the N-type copper indium gallium selenide semiconductor is made of copper indium gallium selenide material and has a chemical formula of Cu(In x Ga 1-x )Se2, of which 0.6 < x < 0.

9.

3. A method for manufacturing a PN junction according to claim 1 or 2, comprising the following steps: (a) using a plurality of continuous vacuum magnetron sputtering coating chambers to coat a P-type copper indium gallium selenide semiconductor thin film layer and an N-type copper indium gallium selenide semiconductor thin film layer one by one using a target material containing one or more of copper, indium, gallium and selenium elements; and (b) performing rapid annealing at a temperature in the range of 350° C. to 450° C. in an inert gas atmosphere, The annealing process uses a green laser or an electric heater as a heating source, and the method described is a dry process and does not require selenization treatment. The method according to claim 3 , wherein the PN junction is fabricated on a flexible substrate.

5. A semiconductor thin film component comprising the PN junction according to claim 1 or 2. 6 . The semiconductor thin film component according to claim 5 , wherein the component is a photodiode component, further comprising a metal anode thin film layer, a transparent metal oxide conductive thin film layer and a transparent metal oxide cathode thin film layer.

7. The semiconductor thin film component according to claim 6, further comprising a layer containing a molybdenum metal compound.

8. A semiconductor thin film component according to claim 7, wherein the layer containing molybdenum metal compounds comprises molybdenum dioxide (MoO2), molybdenum diselenide (MoSe2) or a molybdenum metal compound doped with trace amounts of at least one of lithium, sodium, potassium, rubidium and cesium elements. 9 . The semiconductor thin film assembly according to claim 6 , further comprising a light conversion thin film layer that emits light having a wavelength in the range of 350 nm to 1300 nm.

10. The semiconductor thin film assembly according to claim 9, wherein the light conversion thin film layer emits light having a wavelength of 700 nm to 1100 nm.

11. The semiconductor thin film assembly according to claim 9, wherein the light conversion thin film layer comprises a light emitting material selected from the group consisting of quantum dots, organic phosphorescent or fluorescent materials, and rare earth materials.

12. The semiconductor thin film component according to claim 8, wherein the layer system containing the molybdenum metal compound is located between the metal anode thin film layer and the P-type copper indium gallium selenide semiconductor thin film layer in the PN junction.

13. A photoelectric sensing module, comprising the semiconductor thin film component according to any one of claims 5 to 12.

14. According to the photoelectric sensing module of claim 13, the semiconductor thin film component is a semiconductor thin film photodiode component, and the photoelectric sensing module further comprises a semiconductor thin film transistor component and a semiconductor light emitting component, wherein the semiconductor thin film component, the semiconductor thin film transistor component and the semiconductor light emitting component are integrated and manufactured on the same substrate.

15. The photoelectric sensing module according to claim 14, wherein the material of the metal anode film layer in the semiconductor thin film photodiode component and the material of the source and drain electrodes in the semiconductor thin film transistor component are the same molybdenum metal compound. 16 . The photoelectric sensing module according to claim 14 , wherein the semiconductor light emitting component is an X-RAY, UVLED, IR LED, IR LD or RGB OLED light source.

17. Use of the photoelectric sensing module according to any one of claims 13 to 16 for biometric identification, infrared imaging night vision system sensing, near-infrared photoelectric switch or X-ray sensing.

Images