CN117080292A - Photoelectric device based on p-type doped group 12-16 semiconductor and production method thereof - Google Patents

Photoelectric device based on p-type doped group 12-16 semiconductor and production method thereof Download PDF

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CN117080292A
CN117080292A CN202210509337.XA CN202210509337A CN117080292A CN 117080292 A CN117080292 A CN 117080292A CN 202210509337 A CN202210509337 A CN 202210509337A CN 117080292 A CN117080292 A CN 117080292A
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group
doping
semiconductor
semiconductor layer
light
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彭寿
马立云
殷新建
傅干华
丹尼尔·梅诺斯
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China Triumph International Engineering Co Ltd
CTF Solar GmbH
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China Triumph International Engineering Co Ltd
CTF Solar GmbH
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    • H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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Abstract

The application provides a method for manufacturing an optoelectronic device based on p-type doped group 12-16 semiconductor, which at least comprises the following steps: a) providing a substrate, b) forming a group 12-16 semiconductor layer, c) forming at least one doping source layer, and d) performing a light-assisted treatment, wherein the at least one doping source layer is formed before, after and/or during step b), and the at least one doping source layer comprises at least one doping element selected from group 11 and group 15. The application further provides an optoelectronic device based on a p-doped group 12-16 semiconductor, comprising at least a substrate,and a p-type doped group 12-16 semiconductor layer, the p-type doped group 12-16 semiconductor layer including at least one doping element selected from group 11 and group 15 elements, wherein the concentration of the doping element is 10 13 cm ‑3 To 10 19 cm ‑3 Range.

Description

Photoelectric device based on p-type doped group 12-16 semiconductor and production method thereof
Technical Field
The present application relates to a method of producing an optoelectronic device based on p-type doped group 12-16 semiconductor and an optoelectronic device based on p-type doped group 12-16 semiconductor.
Background
P-type doping of group 12-16 semiconductors is a critical process associated with drawbacks such as low hole carrier concentration or lack of long term stability. Accordingly, there is a need to develop alternative methods for p-doped group 12-16 semiconductor based photovoltaic devices.
US 2009/0133 745 A1 discloses a photovoltaic cell and a process for its production, wherein the photovoltaic active semiconductor material is P-type doped ZnTe doped with As or P element and a specific part of the tellurium ions is replaced by halogen ions. The p-type doped ZnTe absorber layer can be produced by sputtering doped target ZnTe or by electroless deposition of an aqueous solution comprising ions of Zn, te and Mn and doping elements.
EP 2 337,088 A2 discloses a method of p-doping cadmium telluride (CdTe) wherein CdTe has an interface region and at least a portion of the interface region is heat treated in the presence of a first material comprising a p-type dopant such as Bi, P, as, sb, au, ag or Cu and a second material comprising a halogen such as cadmium chloride, hydrochloric acid or chlorine gas.
JP 2002 305 a discloses a method of doping a ZnTe-based compound semiconductor using a first n-type doping material such As Al, ga, and In and a second p-type doping material such As N, P and As, wherein the number of atoms of the second doping material is smaller than the number of atoms of the first doping material.
Disclosure of Invention
It is an object of the present application to provide a method of manufacturing an optoelectronic device based on p-type doped group 12-16 semiconductors.
The object is achieved by the solutions of the independent claims. Preferred embodiments are given in the dependent claims.
The method of manufacturing an optoelectronic device based on p-doped group 12-16 semiconductor according to the present application comprises at least the steps of:
a) A substrate is provided and a substrate is provided,
b) Forming a group 12-16 semiconductor layer,
c) At least one doping source layer is formed and,
d) The light-assisted treatment is carried out and,
wherein the at least one doping source layer is formed before, after and/or simultaneously with step b) and the at least one doping source layer comprises at least one doping element selected from group 11 and group 15 elements.
According to the application, substrate means any base of the semiconductor layer formed in step b). That is, the substrate may include a transparent base substrate, such as glass, a transparent front electrode, and other layers, such as a buffer layer, a window layer, or any other layer. In other embodiments, the substrate may include a transparent or opaque back electrode and other layers, such as a buffer layer or any other layer. That is, the substrate may be a glass, polymer, metal or ceramic material or any other material.
The group 12-16 semiconductor layer refers to a semiconductor including at least one group 12 element such as Zn or Cd and at least one group 16 element such as Se or Te. A non-limiting example of a group 12-16 semiconductor is ZnTe, cdTe, cdSe, cdSeTe. In an embodiment, a group 12-16 semiconductor layer may be formed on a provided substrate with the aforementioned layers on top of the substrate using any technique known in the art, including but not limited to physical vapor deposition, such as sputtering, evaporation or sublimation, electrodeposition, or any other technique. In embodiments, the semiconductor layer may be formed layer-by-layer as a layer stack, such as by depositing one or more CdSe and CdTe layers, and then interdiffusing in the different layers as desired, or by having the above steps completed in the same process. In addition, a process of changing the composition of the surface portion of the semiconductor layer may be performed, for example, by NP etching (phosphorus nitride etching) to form a Te-rich surface on the CdTe-based semiconductor layer. In other embodiments, the semiconductor layer formed has a thickness of 1 μm to 5 μm, preferably 2 μm to 3 μm.
In an embodiment, the method further comprises step e): and (5) performing an activation treatment. Such an activation treatment can induce recrystallization, for example, in CdTe-based semiconductors, reduce lattice defects and improve p-n junctions or their formation. In an embodiment, the activation treatment is performed after the formation of the semiconductor layer in step b). In other embodiments, step e) is performed before, after or during the light assisted treatment in step d). Furthermore, this step may improve the intermixing of the different compounds and/or elements, thereby forming a mixed or doped compound. The activation treatment may include heat treatment and/or treatment with a chemical activator. The activation treatment is known in the prior art, however, the parameters of the activation treatment according to the application may differ from the parameters of the prior art. Such parameters may be, for example, temperature, time or duration, type or amount of chemical activator, or composition and pressure of the surrounding atmosphere. During the activation treatment, the stacked layers, including at least the substrate and the absorber layer (and in some embodiments the doped layer and/or the layer comprising the activator) reach a temperature in the range of 200 ℃ to 500 ℃. However, since the light assisted treatment may be performed before, after or during the activation treatment, the temperature of the stack may be reduced relative to the prior art.
According to the application, at least one doping source layer is formed before, after and/or during step b), and said at least one doping source layer comprises at least one doping element selected from the group 11 and group 15 elements. Advantageously, the doping source layer may be incorporated at any location within the semiconductor layer, so as to provide a gradient or even distribution of doping elements within the semiconductor layer, even with a well-defined degree of doping at certain specific locations within the semiconductor layer, for example at the first or second interface of the semiconductor layer. Forming at least one doping source layer before or after step b) is advantageous for achieving a well-defined doping level, such as a higher doping element concentration. Thereby achieving a higher doping element concentration at the first or second interface of the semiconductor layer.
The group 11 element means an element selected from group 11 of the periodic table, such as Cu, ag and Au, preferably Ag.
Group 15 elements refer to elements selected from group 15 of the periodic table, such As N, P, as, sb and Bi, preferably As.
According to the application, step d) is a light assisted process. In embodiments, the light assisted treatment in step d) is performed during step b), after step b) and step c), before, after or during the activation treatment in step e).
Due to the light assisted treatment, an additional internal electric field is formed in the semiconductor layer, wherein this additional internal electric field provides a drift potential for the charged particles and thus causes a controlled diffusion of these charged particles in the semiconductor layer. The additional internal electric field is additional in that it is added to the internal electric field caused by the pn junction in the semiconductor layer. The diffusion of the charged particles is controlled by the strength and duration of the additional internal electric field. In addition, the photo-assisted treatment, in particular with wavelengths in the UV region, may also promote dissociation of molecular species, wherein these dissociated species are able to diffuse within the additional electric field formed by the photo-assisted treatment. The photo-assisted treatment of the method of the application facilitates the formation of semiconductor layers by interdiffusion and rearrangement mechanisms of atoms, molecules, clusters of molecules, or charged particles (e.g., ions, charge carriers, and/or dopants within the semiconductor material), thereby improving semiconductor quality by reducing existing energy traps and recombination centers. In addition, the light assisted treatment may raise the temperature within the irradiated material by 100 ℃ to 500 ℃ further facilitating the diffusion of the particles. The concentration of at least one doping element in the semiconductor layer can be made to reach 10 by the method 13 cm -3 To 10 19 cm -3 。
Although the application relates in particular to the treatment of a semiconductor layer with light, it should be noted that any electromagnetic radiation capable of inducing an additional internal electric field within the semiconductor layer may be used for the light-assisted treatment. Furthermore, the light assisted treatment may be supported by an external electromagnetic field, which is provided, for example, by a plate capacitor, wherein the semiconductor layer is distributed between its plates, or by applying a voltage on at least one side of the semiconductor layer. In some cases, the light assisted treatment may even be replaced by providing an external electromagnetic field.
Optoelectronic means any known device that can be used as an electro-optic or photoelectric converter, such as a photodiode or solar cell, phototransistor, light emitting diode, photodetector.
In embodiments, the light assisted treatment is performed for 10 seconds to 30 minutes, and/or at a wavelength in the range of 300nm to 1100nm, and/or at 50W/m 2 To 5000W/m 2 At light intensities in the range.
In an embodiment, the light assisted treatment is at 1000W/m 2 To 3000W/m 2 Preferably 1000W/m 2 To 2000W/m 2 At light intensities in the range.
In other embodiments, the light assisted treatment is performed for a duration in the range of 10 seconds to 30 minutes, specifically for a duration of 60 seconds to 20 minutes. The person skilled in the art will know how to adjust the duration of the light assisted treatment in dependence of wavelength and photon energy, i.e. shorter duration in case of higher photon energy and longer duration in case of lower photon energy.
The light may comprise the full length spectrum in the mentioned range, i.e. from UV to IR (infrared), or may comprise only some specific wavelengths or sub-ranges in the mentioned range. If a particular wavelength or sub-range is used, it may be used simultaneously or consecutively.
The light for the light-assisted treatment may be provided by any known light source suitable for providing light having the mentioned intensities and wavelengths, such as a halogen lamp, a light emitting device, a flash lamp or a laser.
In embodiments, the light assisted treatment may be performed from a first interface of the semiconductor layer oriented towards the substrate and/or from a second interface of the semiconductor layer oriented away from the substrate. That is, light may be radiated onto the semiconductor layer from either side in the thickness direction of the optoelectronic device. The thickness direction is a direction in which the substrate and the semiconductor layer overlap each other.
By selecting the particular side of the optoelectronic device corresponding to the material of the substrate and semiconductor layer, the wavelength emitted by the light source and its illumination intensity, the incoming photons can be absorbed at different locations and depths inside the irradiated material. Thus, the strength of the additional internal electric field can be adjusted.
For example, if light passes through the glass substrate and the starting material layer, it may be partially absorbed before reaching the semiconductor region for establishing an electric field.
In an embodiment, the light assisted treatment is performed by a light source, wherein the light source may comprise a plurality of light sources, each light source emitting a wavelength in the range of 300nm to 1100nm and an intensity of 500W/m 2 To 4000W/m 2 Light in the range. The distribution of the light sources may be such that a first interface of the semiconductor layer oriented towards the substrate and/or a second interface oriented away from the substrate is illuminated by the light sources.
In other embodiments, the light assisted treatment is performed under vacuum, under atmospheric conditions, or under controlled atmospheric pressure conditions, such as in an oxygen atmosphere, an argon atmosphere, under chlorine, hydrogen, or nitrogen, or combinations thereof. The controlled atmosphere may also be under reduced pressure relative to atmospheric pressure, e.g. 100mbar (10 4 Pa) or less. The controlled gas pressure conditions may also include the presence of dopants, such As vapors of As, sb or P.
Vacuum refers to pressure of 10 around the semi-finished solar cell -7 mbar(10 -5 Pa) to 10 -1 In the mbar (10 Pa) range.
Atmospheric conditions mean normal air at normal pressure.
In other embodiments, the semifinished productThe periphery of the solar cell may comprise hydrogen and may have a thickness of 1mbar (100 Pa) to 100mbar (10 4 Pa). The presence of hydrogen in the atmosphere has the advantage that, for example, the oxidation state of the dopant species in the activated absorber layer can be changed, and other oxidizing or reducing atmospheres can have the same effect of changing the oxidation state of the species within the absorber.
For example, the first interface of the semiconductor layer in the thin film solar cell device refers to a solar-facing semiconductor layer interface in the thin film solar cell device in a superstrate configuration or a solar-non-facing semiconductor layer interface in the thin film solar cell device in a substrate configuration.
As another example, the second interface of the semiconductor layer in the thin film solar cell device refers to a non-sunlight-facing semiconductor layer interface in the thin film solar cell device in a superstrate configuration or a sunlight-facing semiconductor layer interface in the thin film solar cell device in a substrate configuration.
In embodiments, the light assisted treatment is performed after step b), during step b), after step b) and step c), or before or during the activation treatment.
In an embodiment, if the light assisted treatment is performed during another step (e.g. step b) or the activation treatment), it is meant that the light assisted treatment is performed during the whole duration or at least part of the duration of this step.
In an embodiment, the at least one doping source layer is formed as a compound doping source layer. The compound doping source layer includes at least one doping element selected from group 11 and group 15 elements. Some non-limiting examples of compounds comprising at least one group 11 element (e.g., ag) are Cd x Mg 1-x Te:Ag、Cd x Mg 1-x Se:Ag、Cd x Mg 1-x S:Ag、Zn x Mg 1-x Te:Ag、Zn x Mg 1-x Se:Ag、Zn x Mg 1-x S:Ag、Ag 2 Se、Ag 2 S and Ag 2 Te, wherein x varies between 0.01 and 0.99. Some non-limiting examples of compounds comprising at least one group 15 element (e.g., as) are As 2 Te 3 、As 2 Se 3 And As 2 Se x Te y Wherein x, y varies between 0.01 and 0.99.
In an embodiment, in step b) a CdSeTe semiconductor layer is formed and said at least one doping source layer comprises at least one doping element selected from group 11. Advantageously, photovoltaic devices based on p-type doped CdSeTe semiconductors are formed.
The CdSeTe layer is CdSe-containing x Te 1-x Layers of the composition, wherein x varies between 0 and 1, preferably between 0 and 0.4. The formation of such CdSeTe layers can be performed by: at least one layer of CdSe and at least one layer of CdTe are deposited and the deposited layers are annealed to promote intermixing between cadmium, selenium and tellurium by diffusion. According to the application, intermixing is achieved by a light assisted treatment and thus CdSe formation x Te 1-x And a semiconductor layer.
In an embodiment, the ZnTe semiconductor layer is formed in step b) and the at least one doping source layer comprises at least one doping element selected from group 15. Advantageously, optoelectronic devices based on p-type doped ZnTe semiconductors are formed.
Another aspect of the present application provides a p-doped group 12-16 semiconductor-based photovoltaic device comprising at least a substrate, and a p-doped group 12-16 semiconductor layer, the p-doped group 12-16 semiconductor layer comprising at least one doping element selected from group 11 and group 15, wherein the at least one doping element has a concentration of 10 13 cm -3 To 10 19 cm -3 Within the range.
Such group 12-16 semiconductor photovoltaic devices are capable of achieving higher concentrations of p-doped elements than the prior art, thereby improving semiconductor performance, such as photovoltaic efficiency in semiconductor thin film solar cell devices. Such optoelectronic devices may further include a gradient distribution or well-defined doping level at specific locations within the semiconductor layer.
In an embodiment, the group 12-16 semiconductor layer includes CdSeTe, and at least one doping element therein is a group 11 element.
In an embodiment, the group 12-16 semiconductor layer includes ZnTe, and at least one doping element therein is a group 15 element.
The application also provides the use of the method of the application in the manufacture of a thin film solar cell device based on p-type doped group 12-16 semiconductor.
The p-type doped group 12-16 semiconductor based thin film solar device of the present application has improved semiconductor quality, higher doping element concentration, and thus has improved overall photovoltaic efficiency.
The application is advantageously implemented in combination with the technical features described in the embodiments and in the claims. However, the embodiments of the present application described in the above specification are examples given by way of explanation, and the present application is by no means limited thereto. Any modifications, variations, and equivalent arrangements should be considered to be included within the scope of the present application.
Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a wide variety of alternate and/or equivalent implementations may be substituted for the specific embodiments shown and described without departing from the scope of the present application. This disclosure is intended to cover any adaptations or variations of the specific embodiments discussed herein. Therefore, it is intended that this application be limited only by the claims and the equivalents thereof.
Drawings
The accompanying drawings are included to provide a further understanding of embodiments of the application, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the application and together with the description serve to explain the principles. Other embodiments and many of the intended advantages of the present application will be readily appreciated as they become better understood by reference to the following detailed description. Elements of the drawings are not necessarily drawn to scale relative to each other. Like reference numerals designate corresponding similar parts.
Fig. 1 is a flow chart of an exemplary embodiment of the method of the present application.
Fig. 2 is a flow chart of another exemplary embodiment of the method of the present application.
Detailed Description
Figure 1 shows a flow of one embodiment of the method according to the application. In a first step S10, a substrate is provided. The substrate may be any suitable substrate containing the electrodes and buffer layers required for the optoelectronic device. In the subsequent step S20, a group 12-16 semiconductor layer is formed on the provided substrate. After the photo-assisted and activation treatments, cdSe and CdTe layers are alternately deposited to form CdSe x Te 1-x And a semiconductor layer, thereby forming a group 12-16 semiconductor. Then, in step S30, at least one doping source layer including group 11 doping element Ag is formed on the semiconductor layer as Ag 2 Compound layer of Te. After the formation of the semiconductor layer and the dopant source layer, the light-assisted treatment of step S40 is performed, wherein the light intensity is 1000W/m 2 The wavelength of the light is 300nm to 800nm and the duration is 10 minutes. In embodiments, the activation treatment occurs after S40 or concurrently with S40. The photovoltaic device of the present application requires further processing compared to the prior art. The photovoltaic device fabricated by this embodiment includes Ag doped CdSe x Te 1-x A semiconductor layer of the CdSe oriented away from the substrate x Te 1-x The second interface of the semiconductor layer has a higher Ag concentration.
Fig. 2 shows a flow of another embodiment of the method according to the application. In a first step S10, a substrate is provided. The substrate may be any suitable substrate that contains the electrodes and buffer layers required for the optoelectronic device. In step S30, the at least one doping source layer including the group 15 element As is formed As As after step S10 2 A Te compound layer to achieve a higher doping element concentration at a first interface of the semiconductor layer oriented towards the substrate. Then, in step S20, a ZnTe semiconductor layer is formed by sputtering on As 2 Forming a group 12-16 semiconductor layer on the Te doped source layer, followed by performing a light assist treatment in step S40, wherein the light intensity is 1000W/m 2 The wavelength of the light is 300nm to 800nm and the duration is 10 minutes.

Claims (10)

1. A method of manufacturing a p-type doped group 12-16 semiconductor based optoelectronic device comprising at least the steps of:
a) A substrate is provided and a substrate is provided,
b) Forming a group 12-16 semiconductor layer,
c) At least one doping source layer is formed and,
d) The light-assisted treatment is carried out and,
wherein the at least one doping source layer is formed before, after and/or during step b) and the at least one doping source layer comprises at least one doping element selected from group 11 and group 15.
2. The method according to claim 1, wherein the light-assisted treatment has a duration of 10 seconds to 30 minutes and a wavelength in the range of 300nm to 1100nm and/or a light intensity of 50W/m 2 To 5000W/m 2 Within the range.
3. The method according to claim 1 or 2, characterized in that the light-assisted treatment is performed after and during step b) and before and during the activation treatment.
4. A method according to any one of claims 1 to 3, wherein the at least one doping source layer is formed as a compound doping source layer.
5. The method according to any one of claims 1 to 4, wherein in step b) a CdSeTe layer is formed and said at least one doping source layer comprises at least one doping element selected from group 11.
6. Method according to any one of claims 1 to 5, characterized in that in step b) a ZnTe layer is formed and said at least one doping source layer comprises at least one doping element selected from group 15.
7. An optoelectronic device based on p-type doped group 12-16 semiconductor, comprising at least:
a substrate;
a p-type doped group 12-16 semiconductor layer comprising at least one doping element selected from group 11 and group 15,
wherein the concentration of the doping element is 10 13 cm -3 To 10 19 cm -3 Within the range.
8. The optoelectronic device of claim 7, wherein the group 12-16 semiconductor layer comprises CdSeTe and the doping element is a group 11 element.
9. The optoelectronic device of claim 7, wherein the group 12-16 semiconductor layer comprises ZnTe and the doping element is a group 15 element.
10. Use of the method according to any one of claims 1 to 6 for the manufacture of a thin film solar cell device based on p-type doped group 12-16 semiconductor.
CN202210509337.XA 2022-05-10 2022-05-10 Photoelectric device based on p-type doped group 12-16 semiconductor and production method thereof Pending CN117080292A (en)

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