阅读说明：本技术 Pn接面及其制备方法及用途 (PN junction and preparation method and application thereof ) 是由 高亮 张准 林于庭 于 2019-04-03 设计创作，主要内容包括：本申请涉及一种PN接面及其制备方法及用途,包含所述的PN接面的半导体薄膜组件(尤其是光电二极管组件)及包含所述的半导体薄膜组件的光电感测模块及其广泛用途。所述的PN接面包含P型铜铟镓硒半导体薄膜层及N型铜铟镓硒半导体薄膜层,所述的N型铜铟镓硒半导体薄膜层由铜铟镓硒等元素构成,其中铜相较于铟的莫耳数比在1.1至1.5的范围内且具有化学式Cu(In<Sub>x</Sub>Ga<Sub>1-x</Sub>)Se<Sub>2</Sub>,其中x的数值在0.6至0.9的范围内。制备所述的PN接面的方法使用四元靶材、为干式制程、无须硒化处理且可将所述的PN接面制作于可挠性基板上。(The application relates to a PN junction and a preparation method and application thereof, a semiconductor thin film component (especially a photodiode component) comprising the PN junction, a photoelectric sensing module comprising the semiconductor thin film component and wide application thereof. The PN junction comprises a P-type CIGS semiconductor thin film layer and an N-type CIGS semiconductor thin film layer, wherein the N-type CIGS semiconductor thin film layer is composed of elements such as CIGS, and the like, wherein the molar ratio of copper to indium is In the range of 1.1-1.5, and the chemical formula of the copper (In) is Cu x Ga 1‑x )Se 2 Wherein x has a value in the range of 0.6 to 0.9.The method for preparing the PN junction uses a quaternary target material, is a dry process, does not need selenization treatment and can manufacture the PN junction on a flexible substrate.)

1. A PN junction comprises a P-type CIGS semiconductor thin film layer and an N-type CIGS semiconductor thin film layer.

2. The PN junction according to claim 1, wherein the atomic mole ratio of copper to indium in the P-type cigs semiconductor thin film layer is in the range of 1.6 to 2.

3. The PN junction according to claim 1, wherein the atomic mole ratio of Cu to in the thin film layer of CIGS semiconductor is in the range of 1.1 to 1.5.

4. The PN junction according to any one of claims 1 to 3, wherein the N-type CIGS semiconductor is made of CIGS material and has the chemical formula Cu (In)_xGa_1-x)Se₂Wherein 0.6<x<0.9。

5. A method of manufacturing the PN junction according to any one of claims 1 to 4, comprising the steps of:

(a) plating a P-type CIGS semiconductor thin film layer and an N-type CIGS semiconductor thin film layer one by using a target containing one or more elements such as copper, indium, gallium, selenium and the like through a plurality of continuous vacuum magnetron sputtering coating chambers; and

(b) performing a rapid anneal at a temperature in a range of 350 ℃ to 450 ℃ in an inert gas atmosphere, wherein the anneal uses a green laser or an electric heater as a heating source, and wherein the process is a dry process and does not require selenization.

6. The method of claim 5, wherein the PN junction is formed on a flexible substrate.

7. A semiconductor thin film device comprising the PN junction according to any one of claims 1 to 4.

8. The semiconductor film assembly of claim 7 wherein the assembly is a photodiode assembly further comprising a metal anode film layer, a transparent metal oxide conductive film layer, and a transparent metal oxide cathode film layer.

9. The semiconductor thin film assembly of claim 8, further comprising a layer comprising a molybdenum metal compound.

10. The semiconductor thin film assembly of claim 9, wherein the layer comprising a molybdenum metal compound comprises molybdenum dioxide (MoO)₂) Molybdenum diselenide (MoSe)₂) Or a molybdenum metal compound doped with at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium in a trace amount.

11. The semiconductor thin film assembly of claim 8, further comprising a light conversion thin film layer that emits light having a wavelength in a range of 350nm to 1300 nm.

12. The semiconductor thin film assembly of claim 11, wherein the light conversion thin film layer emits light having a wavelength of 700nm to 1100 nm.

13. The semiconductor thin film assembly of claim 11, 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.

14. The semiconductor film assembly of claim 10 wherein the layer comprising a molybdenum metal compound is between the metal anode film layer and the P-type CIGS semiconductor film layer in the PN junction.

15. A photo-sensing module comprising a semiconductor thin film element according to any one of claims 7 to 14.

16. The module of claim 15, wherein the semiconductor thin film device is a semiconductor thin film photodiode device, the module further comprising a semiconductor thin film transistor device and a semiconductor light emitting device, wherein the semiconductor thin film device, the semiconductor thin film transistor device and the semiconductor light emitting device are fabricated on a same substrate.

17. The module of claim 16, wherein the material of the metal anode thin film layer of the semiconductor thin film photodiode element and the material of the source/drain electrodes of the semiconductor thin film transistor element are the same molybdenum metal compound.

18. The photo-sensing module according to claim 16, wherein the semiconductor light emitting element is an X-RAY, UVLED, IR LED, IR LD or RGB OLED light source.

19. Use of the photo-sensing module according to any one of claims 15 to 18 for biometric identification, infrared image night vision system sensing, near infrared photo-electric switch or X-ray sensing.

Technical Field

The present application relates to a PN junction and a method for preparing the same, a semiconductor thin film device (especially a photodiode device) comprising the PN junction, a photo-sensing module comprising the semiconductor thin film device, and a wide range of applications thereof.

Background

The CIGS semiconductor film has excellent light-sensitive characteristics to visible light, and has better light-sensitive capability to light in the range from infrared light to near infrared light (780-1100 nm) compared with common semiconductor film materials. Therefore, the CIGS semiconductor thin film can be used to fabricate a broadband photodiode assembly.

The conventional cigs photodiode assembly includes (1) a metal electrode thin film layer as an anode, (2) a P-type cigs 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 (fig. 1).

The metal electrode thin film layer as the anode is often prepared by sputtering molybdenum metal.

The P-type CIGS semiconductor thin film layer with high photoelectric conversion characteristics as a light absorption layer is obtained by depositing a CIGS thin film on a substrate plated with a metal anode thin film layer and then performing a selenization process in a way of vacuum magnetron sputtering coating, vacuum co-evaporation coating, printing coating or electroplating coating and the like by using a binary, ternary or quaternary compound target of elements such as copper, indium, gallium, selenium and the like. The selenization process is the most important process in the copper indium gallium selenide process, and aims to improve the proportion of selenium so as to improve the surface energy gap of the component and further solve the problem of over low open circuit voltage. The selenization process also determines the grain size and composition distribution of the CIGS, thereby affecting the photoelectric conversion efficiency of the CIGS. The selenization process is mainly to convert the metal precursor into the selenide semiconductor material under the chemical atmosphere of selenium. The conventional selenization processes are divided into two types, namely Rapid Thermal Processing (RTP) selenization and hydrogen selenide (H2Se) Thermal processing. The RTP heat treatment uses a solid selenium source for heating, and has the advantages of high production speed and difficult control of atmosphere uniformity, so that the efficiency is not high because the composition of crystal grains cannot be adjusted. The heat treatment of H2Se using hydrogen selenide for selenization has the advantage of controlling the atmosphere and thus obtaining a high efficiency module, and the disadvantage of slow production rate of the batch tubular furnace reaction resulting in long reaction times (8-10 hours).

The N-type compound semiconductor thin film layer as the buffer layer must be matched with 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 a high-energy sputtering coating process in the subsequent process and can protect the crystal structure in the light absorbing layer. The P-type CIGS semiconductor thin film layer has a direct energy gap, the surface of the P-type CIGS semiconductor thin film layer can be doped with gallium or sulfide ions to improve the energy gap, and cadmium sulfide (CdS) is often used as a material of an N-type compound semiconductor layer. However, in view of environmental protection, a semiconductor thin film device including an N-type compound semiconductor layer free from cadmium is required.

CN 108470783a discloses a photosensitive device, which comprises 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 CIGS thin film is about 1.37eV, and the intrinsic CIGS thin film has a chemical structure of beta-Cu_0.49(In_0.56Ga_0.44)₃Se₅. Therefore, the characteristic of the CIGS thin film plating needs excessive selenium element, can be achieved by using a high-temperature selenizing process, and cannot be achieved by only using a sputtering or evaporation plating method. In the PIN photosensitive assembly, the P-type CIGS semiconductor thin film layer is formed by plating an intrinsic CIGS thin film layer, contacting with a copper or copper alloy electrode, and performing high-temperature annealing to diffuse copper elements of the electrode into the intrinsic CIGS thin film layer. The diffusion depth of the copper element in the manufacturing method is insufficient, so that a defect structure is generated on the interface between the metal electrode and the P-type copper indium gallium selenide semiconductor film layer, and good ohmic contact cannot be formed. In addition, CN 108470783a proposes an intrinsic copper indium gallium selenide thin film layer, which is mainly used for absorbing light, so that the received light forms an electron-hole pair, and then forms a current through a built-in electric field of a PIN structure to convert the current into an electrical signal. However, intrinsic CIGS thin film layers have very many crystal structure defects, and the patent states that the thickness of the intrinsic CIGS thin film layer ranges from three hundred nanometers to three thousand nanometers, and that P-type CIGS thin film layersThe semiconductor thin film layer and the N-type CIGS semiconductor thin film layer are fifty nanometers to three hundred nanometers, so that the intrinsic CIGS thin film layer has a plurality of internal defect structures. The defect structure can cause the forming efficiency of the electron-hole pairs to be low, and the metal electrode cannot form good ohmic contact with the bonding surface of the P-type CIGS semiconductor thin film layer, so that the built-in electric field cannot effectively separate the electron-hole pairs to form carrier current, and the PIN CIGS component structure cannot effectively operate. In addition, since intrinsic cigs is thermodynamically unstable and is easily phase-separated during annealing, it is difficult to reduce structural defects by annealing.

The selenization process of the P-type copper indium gallium selenide semiconductor thin film layer and the plating of the N-type compound semiconductor layer using cadmium sulfide both involve high-temperature chemical reactions, so that the structure inside the thin film is affected, and the photoelectric conversion efficiency of the generated photodiode assembly is damaged. Therefore, there is a need in the art for a cadmium-free PN junction that does not require selenization and is suitable for use in semiconductor thin film devices.

Disclosure of Invention

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

It is another object of the present invention to provide a semiconductor thin film device, in particular a semiconductor photodiode device, comprising said PN junction. According to one embodiment of the present invention, the semiconductor thin film photodiode assembly further comprises a layer comprising a molybdenum metal compound. According to another embodiment of the present invention, the semiconductor thin film photodiode assembly further comprises a light conversion thin film layer emitting light having a wavelength of 350nm to 1300 nm. According to still another embodiment of the present invention, the semiconductor thin film photodiode assembly further comprises a layer containing a molybdenum metal compound and a light conversion thin film layer emitting light having a wavelength of 350nm to 1300nm at the same time.

It is another object of the present invention to provide a photo-sensing module comprising a semiconductor thin film device, particularly a semiconductor thin film photodiode device, having the PN junction.

It is another object of the present invention to provide a use of the photoelectric sensing module for biometric identification, infrared image night vision system sensing, near infrared photoelectric switch or X-ray sensing.

Additional aspects and advantages of embodiments of the present application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the present application.

Drawings

Drawings necessary for describing embodiments of the present application or the prior art will be briefly described below in order to describe the embodiments of the present application. It is to be understood that the drawings in the following description are only some of the embodiments of the present application. It will be apparent to those skilled in the art that other embodiments of the drawings can be obtained from the structures illustrated in these drawings without the need for inventive work.

Fig. 1 shows a photodiode structure including a P-type cigs semiconductor thin film layer in the prior art.

Fig. 2 shows a PN junction according to the present invention.

Fig. 3 is a semiconductor thin film photodiode assembly according to the present invention.

Fig. 4 is an aspect of a semiconductor thin film photodiode assembly according to the present invention that includes a layer comprising a molybdenum metal compound.

Fig. 5 is an aspect of a semiconductor thin film photodiode assembly according to the present invention, which includes a light conversion thin film layer.

Fig. 6 is an aspect of a semiconductor thin film photodiode assembly according to the present invention, which includes both a layer containing a molybdenum metal compound and a light conversion thin film layer.

Fig. 7 is a characteristic curve of current density versus voltage when the photodiode assemblies of the present invention and comparative examples are applied to a solar cell.

Detailed Description

Embodiments of the present application will be described in detail below. Throughout the specification, the same or similar components and components having the same or similar functions are denoted by like reference numerals. The embodiments described herein with respect to the figures are illustrative in nature, are diagrammatic in nature, and are used to provide a basic understanding of the present application. The examples of the present application should not be construed as limiting the present application.

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

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.

As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention, as such, and the language in the specification should not be construed as implying that any non-claimed method or condition may constitute essential features of the invention.

In the detailed description and claims, a list of items connected by the terms "one of," "one of," or other similar terms may mean any one of the listed items. For example, if items a and B are listed, the phrase "one of a and B" means a alone or B alone. 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 comprise a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

In the detailed description and claims, a list of items linked by the term "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 a only; 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 a only; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

The present invention will be described in detail below.

[ PN junction ]

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

(a) a P-type CIGS semiconductor thin film layer; and

(b) and the N-type copper indium gallium selenide semiconductor thin film layer.

The PN junction (figure 2) uses the N-type CIGS semiconductor thin film layer to replace the conventional N-type compound semiconductor thin film layer, so as to achieve the purposes of reducing the selenization process and reducing the process temperature.

a.P type CIGS semiconductor thin film layer

The mole 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 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, excessive Cu is formed in the crystal structure inside the film layer_InAcceptor defects, which affect the light absorption efficiency and the transport capability of hole carriers; when the molar ratio is lower than 1.6, the P-type CIGS semiconductor cannot be generated. The P-type CIGS semiconductor with the mole ratio has lower crystal structure defects, higher light absorption coefficient and hole carrier transmission capability.

According to one aspect of the invention, the P-type CIGS semiconductor material has the chemical formula Cu (In)_xGa_1-x)Se₂Wherein x is more than or equal to 0.5 and less than or equal to 0.625, preferably more than or equal to 0.52 and less than or equal to 0.62. Such as, 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, 0.551, 0.513, 0.517, etc561, 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.

N-type CIGS semiconductor thin film layer

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 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 mole ratio is higher than 1.5, the N-type CIGS semiconductor cannot be generated, and when the mole ratio is lower than 1.1, In the crystal structure In the film layer_CuThe donor defects are excessive and affect the electron carrier transport capability. The N-type CIGS semiconductor with the molar ratio does not need selenization treatment.

According to one aspect of the invention, the N-type CIGS semiconductor material has the chemical formula Cu (In)_xGa_1-x)Se₂Wherein x is more than or equal to 0.63 and less than or equal to 0.9, and preferably x is more than or equal to 0.7 and less than or equal to 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, 0.695, 0.697, 0.699, 0.701, 0.703, 0.705, 0.821, 0.707, 0.713, 0.715, 0.717, 0.723, 0.721, 0.723, 0.701, 0.703, 0.793, 0.779, 0.849, 0.779, 0.849, 0.779, 0.849, 0.777, 0.849, 0.777, 0.779, 0.849, 0.777, 0.849, 0.793, 0.7, 0.777, 0.7, 0.849, 0.777, 0.7, 0.779, 0.849, 0.777, 0.849, 0.7, 0.849, 0.777, 0.7, 0.849, 0.7, 0.793, 0.753. 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.

The PN junction according to the present invention may be used in semiconductor thin film devices such as, but not limited to, semiconductor transistor devices or semiconductor photodiode devices, in particular semiconductor photodiode devices.

[ semiconductor thin film photodiode Assembly ]

The semiconductor thin film photodiode assembly of the present invention comprises the following parts (fig. 3):

(a) a metal electrode thin film layer as an anode;

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

(c) a transparent metal oxide conductive thin film layer as a conductive layer, if necessary; and

(d) a transparent metal oxide thin film layer as a cathode.

The semiconductor thin film photodiode assembly does not need selenization treatment and does not relate to an N-type compound semiconductor layer of cadmium sulfide in the preparation process, so that high-temperature chemical reaction is not involved, the temperature treatment of about 150 ℃ to 450 ℃ can be used, the influence on the structure in the thin film is avoided, and the semiconductor thin film photodiode assembly has higher photoelectric conversion efficiency compared with the traditional photodiode assembly.

a. Metal electrode film layer as anode

The metal anode thin film layer is not particularly limited, and can be any metal electrode material known to one having ordinary skill in the art to which the present invention pertains, such as but not limited to a material containing molybdenum (Mo), such as but not limited to Mo, Ti/Mo, Cr/Mo, Al/Mo, Au/Mo, or a material containing titanium, gold, silver, copper, or chromium.

PN junction

The PN junction is a PN junction according to the invention and comprises a P-type CIGS semiconductor thin film layer used as a light absorption layer and an N-type CIGS semiconductor thin film layer used as a buffer layer. The P-type CIGS semiconductor thin film layer has photoelectric conversion energy as a light absorption layerHigh light absorption coefficient (more than 105 cm)^-1) Light having a wavelength in the range of 350nm to 1300nm, preferably 700nm to 1100nm, more preferably 780nm to 900nm, is absorbed. The N-type CIGS semiconductor thin film layer is used as a buffer layer and is matched with the energy gap of the light absorption layer to form a depletion region with enough thickness, so that the light absorption layer is prevented from being damaged by a high-energy sputtering coating process in the subsequent process, and the crystal structure in the thin film is protected.

c. Transparent metal oxide thin film layer as conductive layer

According to an aspect of the present invention, the transparent metal oxide conductive thin film layer as the conductive layer can be used, but the transparent metal oxide conductive thin film layer as the conductive layer is not particularly limited, and can be any metal electric and material known to those skilled In the art, such as but not limited to i-ZnO/ITO, i-ZnO/AZO, i-ZnO/BZO (ZnO: B), i-ZnO/IWO (In)₂O₃:W)、i-ZnO/IWZO(In₂O₃:W:ZnO)。

d. Transparent metal oxide thin film layer as cathode

The transparent metal oxide thin film layer as the cathode is not particularly limited, and may be any metal electrode and material known to those skilled In the art, such as but not limited to i-ZnO/ITO, i-ZnO/AZO, i-ZnO/BZO (ZnO: B), i-ZnO/IWO (In)₂O₃:W)、i-ZnO/IWZO(In₂O₃:W:ZnO)。

The materials of the transparent metal oxide conductive thin film layer as the conductive layer and the transparent metal oxide thin film layer as the cathode can be the same or different.

According to an aspect of the present invention, the semiconductor thin film photodiode assembly further comprises a layer containing a molybdenum metal compound as a hole transport thin film layer. The hole transmission thin film layer is preferably arranged between the metal anode thin film layer and the P-type CIGS semiconductor thin film layer in the PN junction (figure 4), and is used for reducing the potential between the molybdenum metal thin film anode layer and the P-type CIGS semiconductor thin film layerPoor, thereby improving the efficiency of hole transport to the anode. The hole transport thin film layer is a layer containing a molybdenum metal compound, such as but not limited to molybdenum dioxide (MoO)₂) Molybdenum diselenide (MoSe)₂) Or a molybdenum metal compound doped with at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium in a trace amount.

When the copper indium gallium selenide photodiode is manufactured, alkali metal ions in the soda-lime glass substrate can be diffused into the copper indium gallium selenide semiconductor thin film layer under a high-temperature manufacturing process, so that the electrical property of the semiconductor thin film layer is improved. On the other hand, when manufacturing a thin film transistor, in order to prevent alkali metal ions in the soda-lime glass substrate from diffusing into an oxide layer inside the thin film transistor in a high-temperature process, and further reduce the electrical performance of the thin film transistor, a non-soda-lime glass substrate is often used. The hole transport thin film layer can be conventionally applied to a soda-lime glass substrate, and when the hole transport thin film layer is applied to a non-soda-lime glass substrate, high photoelectric conversion efficiency can be maintained.

According to another aspect of the present invention, the semiconductor thin film photodiode assembly further comprises a light conversion thin film layer (fig. 5). The light conversion thin film layer is mainly used for converting absorbed incident lights with different wavelengths into lights which are easily absorbed by the P-type CIGS semiconductor thin film layer serving as the light absorption layer, such as lights with wavelengths ranging from 350nm to 1300nm, preferably lights with wavelengths ranging from 700nm to 1100nm, and more preferably lights with wavelengths ranging from 780nm to 900nm, so that the light absorption of the P-type CIGS thin film layer is increased, and the photoelectric conversion effect of the photodiode assembly is promoted. The light conversion film layer also has the function of protecting the cathode/transparent conductive oxide film layer from chemical erosion of water vapor and acid-base liquid, so that the service life of the photodiode assembly is prolonged. The material of the light conversion thin film layer is not particularly limited, and may be any light emitting material known to those having ordinary knowledge in the art to which the present invention pertains, such as, but not limited to, a light emitting material including one selected from the group consisting of quantum dots, organic phosphorescent or fluorescent materials, and rare earth materials.

According to another aspect of the present invention, the semiconductor thin film photodiode assembly includes both a layer containing a molybdenum metal compound as a hole transport thin film layer and a light conversion thin film layer (fig. 6).

[ photoelectric sensing Module ]

The photoelectric sensing module of the invention comprises a semiconductor thin film component with a PN junction according to the invention.

According to an aspect of the present invention, the semiconductor thin film device is a semiconductor thin film photodiode device, and the photo-sensing module further includes a semiconductor thin film transistor device and a semiconductor light emitting device.

According to an aspect of the present invention, the semiconductor thin film photodiode element, the semiconductor thin film transistor element and the semiconductor light emitting element are integrated and fabricated on a same substrate.

According to one aspect of the 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.

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

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

The photoelectric sensing module can be used for biological identification, infrared image night vision system sensing, near infrared photoelectric switch or X-ray sensing.

[ preparation method of PN junction ]

The present application provides a method of manufacturing the PN junction, which comprises the steps of:

(a) plating a P-type CIGS semiconductor thin film layer and an N-type CIGS semiconductor thin film layer one by using a target containing one or more elements such as copper, indium, gallium, selenium and the like through a plurality of continuous vacuum magnetron sputtering coating chambers; and

(b) annealing is performed at a temperature in the range of 350 ℃ to 450 ℃ in an inert gas atmosphere,

wherein the coating chamber has two target positions.

The target material may be binary, ternary or quaternary target materials containing one or more elements of copper, indium, gallium, selenium and the like, preferably ternary or quaternary target materials containing elements of copper, gallium, selenium and the like, or quaternary target materials containing elements of copper, indium, gallium, selenium and the like. Such as but not limited to Cu_yGaSe_z、Cu_y(In_xGa_1-x)Se_zWherein 0.5. ltoreq. x.ltoreq.0.9, such as 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. 0.553, 0.555, 0.557, 0.559, 0.561, 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, 0.5919, 0.643, 0.719, 0.103, 0.9, 0.05, 0.35, 0.9, 0.05, 0.9, 0.35, 0.9, 0.05, 0.9, 0.35, 0.9, 0.05, 0.9, 0.35, 0.9, 0.3, 0.35, 0.9, 0.05, 0.9, 0.3, 0.05, 0.3, 0.9, 0.3.9, 0.05, 0.9, 0.3.9, 0.9, 0.3, 0.3.3.3.3, 0.9, 0.05, 0.9, 0.45, 0.9, 0.670.9, 0.05, 0.9, 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, 0.833, 0.825, 0.827, 0.829, 0.831, 0.745, 0.841, 0.839, 0.8384, 0.839, 0.765, 0.777, 0.839, 0.767, 0.839, 0.835, 0.837, 0.73. 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;

wherein y is not less than 0.8 and not more than 1.2, such as 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, 0.033, 0.831, 0.833, 0.835, 0.837, 0.839, 0.841, 0.3, 0.845, 0.847, 0.033849, 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, 0.975, 0.0197, 0.977, 0.973, 0.977, 0.971, 0.973, 0.971.979, 0.973, 0.971.973, 0.7, 0.971.979, 0.971.09, 0.971.7, 0.959, 0.973, 0.971.971.979, 0.971.973, 0.973, 0.971.971, 0.973, 0.971.973, 0.971.971.973, 0.09, 0.971.971.971.979, 0.971.979, 0.979, 0.973, 0.971.979, 0.979, 0.971.979, 0.971.971.979, 0.971.979, 0.979, 0.971.971.971.979, 0.979, 0.971.979, 0.979, 0.971.971.973, 0.979, 0.971.979, 0.971.971.971., 1.041, 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, 1.083, 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, 1.125, 1.127, 1.129, 1.131, 1.133, 1.135, 1.149, 1.141, 1.115, 1.181, 1.5639, 1.185, 1.5639, 1.35185, 1.1.29, 1.185, 1.29, 1.185, 1.35, 1.1.185, 1.1.1.1.1.1.1.1.1.35, 1.1.1.1.1.1.35, 1.35, 1.121, 1.123, 1.35, 1.1.1.1.35, 1.185, 1; and

wherein 1.8 is less than or equal to z is less than or equal to 2.2, such as 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, 1.853, 1.859, 1.853, 1.865, 1.867, 1.869, 1.041871, 1.853, 1.875, 1.877, 1.879, 1.881, 1.853, 36895, 1.853, 36961.971.973, 1.853, 36961.971.973, 36981.971.973, 1.853, 36961.971.971.973, 1.853, 36983, 36961.971.971, 1.853, 36961.971.971.971, 1.853, 363, 36961.971.973, 1.853, 36961.973, 1.853, 363, 36983, 363, 36961.971.971.971.971, 1.853, 36987, 36983, 36961.971, 1.853, 36961.971.971.973, 1.853, 36961.971.971.973, 1.853, 363, 1.853, 36961.971.971.971.971.971.971.971, 1.853, 363, 1.853, 363, 36961.971., 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, 2.083, 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, 2.125, 2.127, 2.129, 2.131, 2.133, 2.135, 2.137, 2.139, 2.141, 2.143, 2.145, 2.147, 2.149, 2.153, 2.155, 2.153, 2.161, 36185, 2.161, 36185, 2.161, or 36185.

Wherein the annealing uses a green laser or an electric heater as a heating source and wherein the process is a completely dry process and does not require selenization.

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

The rapid anneal is not selenizing and does not involve a selenium-containing species. Such as, but not limited to, a green laser or an electric heater.

According to one aspect of the present invention, the annealing time is in the range of 10 to 120 seconds when a green laser is used as a heating source. According to another aspect of the present invention, when the electric heater is used as the heating source, the annealing time is in a range of 180 to 600 seconds.

According to one aspect of the invention, the PN junction is formed on a flexible substrate.

[ method for producing semiconductor thin film photodiode Assembly ]

The semiconductor thin film photodiode assembly is prepared by a vacuum magnetron sputtering coating mode, and when the light conversion thin film layer exists, the light conversion thin film layer is prepared by a spray printing coating mode, a screen printing coating mode, a rotary coating mode, a slit type coating mode, a thermal transfer coating mode or a transfer printing sticking film mode.

Because the temperature is controlled within 450 ℃ and the selenization manufacturing process is not needed, in the manufacturing process of the photodiode component, the chemical reaction effect or the thermal aging effect cannot be generated on the thin film layer structure or the internal metal circuit of the thin film transistor component manufactured on the substrate, so that the two components are integrated on the same substrate to lose the use function. The working procedures in the manufacturing process can be reduced, and the working capacity of the assembly formed by integrating the two assemblies can be ensured.

Preparation example

Preparation of PN junction

1. Placing the substrate In a vacuum coating cavity for coating a P-type CIGS semiconductor film layer, wherein the cavity has two target positions, and the target positions are four-element target materials (Cu (In) containing atoms such as copper, indium, gallium and selenium_0.63Ga_0.27)Se₂). The film is deposited by co-sputtering at a coating rate of 0.1 to 0.2 microns per minute. The film thickness of the obtained P-type CIGS semiconductor film layer is in the range of 1-2 microns;

2. transferring the substrate obtained in the step 1 into a vacuum coating cavity for coating an N-type CIGS semiconductor thin film layer, wherein the cavity is provided with two target positions, and one target position contains copperTernary target material of atoms of gallium, selenium and the like (no In, CuGaSe₂) The other target is a quaternary target containing atoms of copper, indium, gallium, selenium, etc. (Cu (In)_0.63Ga_0.27)Se₂). The film is deposited by co-sputtering at a coating rate of 0.01 to 0.02 microns per minute. The thickness of the obtained N-type CIGS semiconductor thin film layer is in the range of 0.05 micrometer to 0.1 micrometer.

Preparing a semiconductor thin film photodiode assembly including the PN junction

1. Placing a glass substrate in a vacuum coating cavity for coating a molybdenum metal film, heating to 250 ℃, and coating a molybdenum (Mo) metal film layer with the thickness of 0.8 micron by adopting a magnetron sputtering coating mode to serve as a metal electrode film layer of an anode; the pressure in the cavity is 1.0 to 5.0x 10 during film coating^-3In the mbar range;

2. conveying the substrate plated with the molybdenum metal anode film obtained in the step 1 into a vacuum coating cavity plated with sodium molybdate (Mo: Na), and coating the sodium molybdate film with the thickness of 0.01-0.03 micrometer to be used as a hole transmission film layer, wherein the sodium accounts for 12 percent of the total weight of the used sodium molybdate metal compound target;

3. preparing a PN junction on the substrate obtained in the step 2 by using the step of preparing the PN junction;

4. transferring the substrate obtained in the step 3 into a vacuum chamber for rapid annealing, and annealing at a temperature ranging from 350 ℃ to 450 ℃ in an inert gas atmosphere for 100 to 300 seconds;

5. and (3) transferring the substrate obtained in the step (4) into a vacuum coating cavity coated with a transparent metal oxide thin film layer serving as a cathode, wherein the cavity is internally provided with two target positions, firstly, an intrinsic zinc oxide thin film is coated on the N-type copper indium gallium selenide semiconductor thin film layer subjected to rapid annealing treatment, the thickness of the intrinsic zinc oxide thin film is about 0.01 micrometer to 0.02 micrometer, and then, an indium tin oxide thin film is coated on the intrinsic zinc oxide thin film, and the thickness of the indium tin oxide thin film is about 0.01 micrometer to 0.02 micrometer.

The glass substrate/Mo (0.8 micron)/Mo is obtained, wherein the Mo is Na (0.03 micron)/P type-copper indium gallium selenide (2 micron)/N type-copper indium gallium selenide (0.05 micron)micron)/i-ZnO (0.01 micron)/ITO (0.02 micron). When the photodiode assembly is applied to a solar cell, the current density versus voltage characteristic curve is shown in fig. 7, in which the short-circuit current (J) is shown_sc) Is 32.716mA/cm²Open circuit voltage (V)_oc) 649mV, a Fill Factor (FF) of 75.5% and a power generation Efficiency (EFF) of 16.03%.