Nickel oxide doped target, its manufacturing method and use

Abstract

A nickel oxide doped target includes a nickel oxide base material and a doping material that includes at least one of compounds containing one or more of the following elements: Cu, Ca, Cr, Sn, Hg, Pb, Mg, Mn, Ag, Co, and Pr.

Description

[Technical Field]

[0001] This application relates to the technical field of sputtering process targets, and in particular to nickel oxide doped targets and their manufacturing methods and uses. [Background technology]

[0002] In perovskite solar cells, efficient photoelectron transport depends on the performance stability and repeatability of the perovskite hole transport layer (HTL). Currently, there are many materials that can be used as the HTL in perovskite thin film cells, among which nickel oxide is the most common. Currently, the relatively mature technology for manufacturing HTLs is typically by sputtering using a nickel oxide target.

[0003] As the performance requirements for perovskite solar cells increase, how to improve the performance of the hole transport layer is a current research focus. Summary of the Invention

[0004] The present application has been made in view of the above-mentioned problems, and an object of the present application is to provide a novel nickel oxide-doped target and further to realize an improvement in the performance of a hole transport layer produced using the nickel oxide-doped target.

[0005] To achieve the above object, the present application provides a nickel oxide doped target and its manufacturing method and use.

[0006] According to a first aspect of the present application, there is provided a nickel oxide-doped target including a nickel oxide base material and a doping material to be doped, the doping material including at least one of compounds containing one or more elements of Cu, Ca, Cr, Sn, Hg, Pb, Mg, Mn, Ag, Co, and Pr.

[0007] Thus, the present application demonstrates that doping with specific compounds results in a narrower hole transport layer energy band gap, a higher spectral response, and higher cell conversion efficiency in perovskite solar cells fabricated with the present nickel oxide-doped targets, significantly improving the performance of the hole transport layer and perovskite solar cells fabricated with the present targets.

[0008] In any of the embodiments, the dopant includes at least one of CuO, CuO, CuS, CuI, CuSCN, CuGaO, CoO, CrO, SnO, SnS, HgO, PbO, AgO, AgO, MnO, and PrO, which is advantageous in further improving the performance of the hole transport layer and the battery.

[0009] In any of the embodiments, the dopant comprises at least two of CuO, Cu2O, Cu2S, CuI, CuSCN, CuGaO2, CoO, Cr2O3, SnO, SnS, Hg2O, PbO, AgO, Ag2O, MnO, and Pr2O3. The inventors have surprisingly discovered that simultaneous doping of at least two of the dopant compounds further improves the performance of the battery, particularly the conversion efficiency.

[0010] In any one of the embodiments, the content of the dopant in the nickel oxide doped target is 0.1 wt % to 20 wt %.

[0011] In any one of the embodiments, the content of CuO is 0 to 15%, the content of Cu2O is 0 to 15%, the content of Cu2S is 0 to 15%, the content of CuI is 0 to 20%, the content of CuSCN is 0 to 15%, the content of CuGaO2 is 0 to 15%, the content of CoO is 0 to 8%, and the content of Cr2O3 is 0 to 15%, based on the total mass of the nickel oxide-doped target. is 0 to 15%, the content of SnO is 0 to 15%, the content of SnS is 0 to 15%, the content of Hg2O is 0 to 15%, the content of PbO is 0 to 15%, the content of AgO is 0 to 15%, the content of Ag2O is 0 to 15%, the content of MnO is 0 to 10%, the content of Pr2O3 is 0 to 15%, and the total content of the doping substances is 0.1% to 20%.

[0012] In either embodiment, the nickel oxide doped target is obtained by a graded plasma spraying method, which results in a more uniform distribution of dopant within the nickel oxide substrate.

[0013] A second aspect of the present application further provides a method for producing a nickel oxide-doped target, the method comprising: The method includes warm spraying a binding coating layer onto a target backplate or a target backpipe, introducing nickel oxide powder and powders of each dopant into respective plasma-generating spray coaters, and simultaneously plasma spraying the nickel oxide and each dopant onto the target backplate or the target backpipe to obtain the nickel oxide-doped target, wherein the dopant is selected from at least one of compounds containing one or more elements of Cu, Ca, Cr, Sn, Hg, Pb, Mg, Mn, Ag, Co, and Pr.

[0014] The method of the present application allows for flexible control of the type and content of the dopant, thereby enabling nickel oxide-doped targets with different types and contents of dopant to be obtained. Furthermore, the method of the present application is more advantageous in that it allows for the production of nickel oxide-doped targets with a more uniform dopant distribution.

[0015] According to a third aspect of the present application, there is further provided a use of a nickel oxide-doped target according to the first aspect of the present application or a nickel oxide-doped target produced by a method according to the second aspect of the present application in the manufacture of a hole transport layer of a perovskite solar cell.

[0016] The nickel oxide-doped target according to the present application includes one or more doping materials, and the perovskite solar cell manufactured using the nickel oxide-doped target according to the present application has a narrower hole transport layer energy band gap, a higher spectral response, and a higher cell conversion efficiency, indicating that the hole transport layer of the perovskite solar cell for manufacturing the nickel oxide-doped target according to the present application can improve the cell performance. [Brief explanation of the drawings]

[0017] [Figure 1] 1 shows the spectral curves of hole transport layers produced using the nickel oxide-doped target of Example 1 and the nickel oxide target of Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, with appropriate reference to the drawings, embodiments of the nickel oxide-doped target and its manufacturing method and use will be described in detail and specifically disclosed. However, unnecessary details may be omitted. For example, detailed descriptions of well-known matters and redundant descriptions of identical structures may be omitted. This is to avoid unnecessarily lengthening the following description and to facilitate understanding by those skilled in the art. Note that the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0019] "Ranges" disclosed herein are defined in the form of lower and upper limits. A given range is defined by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of that particular range. Such ranges may or may not be inclusive of the endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a single range. For example, if 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 60-110 and 80-120 are also contemplated. Furthermore, if minimum range values ​​1 and 2 are listed and maximum range values ​​3, 4, and 5 are listed, the ranges 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5 are all contemplated. In this application, unless otherwise specified, the numerical range "ab" is a shorthand expression representing any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is merely a shorthand representation of combinations of these numbers. Also, expressing that a parameter is an integer ≧2 is equivalent to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0020] Unless otherwise stated, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0021] Unless otherwise stated, all technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0022] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, when a method includes steps (a) and (b), this means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, when a method is described that further includes step (c), this means that step (c) can be added to the method in any order; for example, the method may include steps (a), (b), and (c), or may include steps (a), (c), and (b), or may include steps (c), (a), and (b), etc.

[0023] Unless otherwise specified, the terms "comprise" and "include" referred to in this application may be open-ended or closed-ended. For example, the terms "comprise" and "include" may further include or include other components not listed, or may include or include only the listed components.

[0024] Unless otherwise stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); Both A and B are true (or exist).

[0025] In the course of researching the fabrication of hole transport layers for perovskite solar cells, the applicant discovered that the performance of the hole transport layer could be improved by doping the nickel oxide thin film, which serves as the hole transport layer, with different elements. However, currently, the target is often a single nickel oxide target, and the fabrication of doped nickel oxide thin films requires co-sputtering with the nickel oxide target and another target, which is a complicated process and makes it difficult to achieve a uniform distribution of the doped elements in the resulting nickel oxide thin film, limiting the fabrication of doped nickel oxide thin films and improving their electrical performance. To further improve the performance of the hole transport layer and thereby improve the performance of perovskite solar cells, the present application provides a nickel oxide-doped target for fabricating the hole transport layer of perovskite solar cells.

[0026] In one embodiment of the present application, the present application proposes a nickel oxide-doped target including a nickel oxide base material and a doping material including at least one of compounds containing one or more elements of Cu, Ca, Cr, Sn, Hg, Pb, Mg, Mn, Ag, Co, and Pr.

[0027] Although the principle is not yet clear, the applicant has unexpectedly discovered that when the nickel oxide-doped target of the present application is used to fabricate a hole transport layer in a perovskite solar cell, the hole transport layer is doped with a compound of a specific element, resulting in a narrower energy band gap, a higher spectral response, and a significantly improved cell conversion efficiency. Furthermore, fabricating a hole transport layer using the nickel oxide-doped target of the present application can effectively improve the manufacturing process window of the doped hole transport layer compared to methods such as co-sputtering, making it easier to achieve thin film process stability and consistency.

[0028] In some embodiments, the dopant comprises at least one of CuO, Cu2O, Cu2S, CuI, CuSCN, CuGaO2, CoO, Cr2O3, SnO, SnS, Hg2O, PbO, AgO, Ag2O, MnO, Pr2O3.

[0029] The inventors discovered that when a simple dopant is selected, the simple element is prone to incomplete reaction with oxygen, making it difficult to control the component composition and doping ratio, and that some simple elements, such as Ga, Ag, Pb, I, and S, are difficult to powder and use in plasma spraying. When the above compounds are directly doped into a nickel oxide substrate as a dopant, the component composition and content can be more easily controlled compared to doping with simple elements, further improving the electrical performance of perovskite solar cells in which a hole transport layer is fabricated using this target.

[0030] In some embodiments, the dopant comprises at least two of CuO, Cu2O, Cu2S, CuI, CuSCN, CuGaO2, CoO, Cr2O3, SnO, SnS, Hg2O, PbO, AgO, Ag2O, MnO, and Pr2O3. The inventors discovered that when at least two of the dopant compounds are simultaneously doped, the resulting composite target contains anions and cations of different valences, which allows for a larger tuning window for the energy level structure of the resulting thin-film solar cell, making energy level tuning easier, and further improving the photoconversion efficiency of the cell.

[0031] In some embodiments, the content of the dopant in the nickel oxide doped target is 0.1 wt% to 20 wt%. The inventors have found that a dopant content within this range is advantageous for improving the performance of the nickel oxide thin film produced, while an excessive amount of the dopant, for example, greater than 20 wt%, reduces the performance of the nickel oxide substrate and is detrimental to improving overall performance.

[0032] In some embodiments, the CuO content is 0-15%, the CuO content is 0-15%, the CuS content is 0-15%, the CuI content is 0-20%, the CuSCN content is 0-15%, the CuGaO content is 0-15%, the CoO content is 0-8%, the CrO content is 0-15%, the SnO content is 0-15%, the SnS content is 0-15%, the HgO content is 0-15%, the PbO content is 0-15%, the AgO content is 0-15%, the AgO content is 0-15%, the MnO content is 0-10%, the PrO content is 0-15%, and the total content of the dopant is 0.1%-20%, based on the total mass of the nickel oxide-doped target. The inventors have discovered that the optimal content ranges of different doping substances for improving the performance of the hole transport layer are different, and each of the above compounds is advantageously doped into the nickel oxide target in the concentration ranges described in this application to improve the performance of the hole transport layer.

[0033] In either embodiment, the nickel oxide doped target is obtained by a graded plasma spraying method, which results in a more uniform distribution of dopant within the nickel oxide substrate.

[0034] The classed plasma spraying described in this application may be understood as different materials, for example nickel oxide and one or more doping materials, each being sprayed independently.

[0035] According to a second aspect of the present application, there is further provided a method for producing a nickel oxide-doped target, the method comprising the steps of: The method includes warm spraying a binding coating layer onto a target backplate or a target backpipe, introducing nickel oxide powder and powders of each dopant into respective plasma-generating spray coaters, and simultaneously plasma spraying the nickel oxide and each dopant onto the target backplate or the target backpipe to obtain the nickel oxide-doped target, wherein the dopant is selected from at least one of compounds containing one or more elements of Cu, Ca, Cr, Sn, Hg, Pb, Mg, Mn, Ag, Co, and Pr.

[0036] The doped nickel oxide target obtained by the method of the present application has a more uniform distribution of the dopant. Furthermore, the method of the present application can significantly improve the relative density of the target and reduce defects inside the target, which results in a more uniform material for the obtained nickel oxide thin film, which is more advantageous for improving the performance of the hole transport layer.

[0037] Furthermore, the method of the present application allows for flexible control of the type and content of dopant, and allows for direct production of targets doped with appropriate concentrations and types of dopant according to different performance requirements of the hole transport layer, so that hole transport layers with the corresponding dopant types and contents can be directly obtained through the sputtering process, thereby realizing convenient and accurate process control.

[0038] Furthermore, the manufacturing method according to the present application is a simple process, has strong controllability, and facilitates rapid and efficient manufacturing molding over a wide range.

[0039] In some embodiments, the dopant is selected from at least one of CuO, Cu2O, Cu2S, CuI, CuSCN, CuGaO2, CoO, Cr2O3, SnO, SnS, Hg2O, PbO, AgO, Ag2O, MnO, Pr2O3.

[0040] In some embodiments, the dopant is selected from at least two of CuO, Cu2O, Cu2S, CuI, CuSCN, CuGaO2, CoO, Cr2O3, SnO, SnS, Hg2O, PbO, AgO, Ag2O, MnO, Pr2O3.

[0041] In some embodiments, the content of the dopant in the nickel oxide doped target is 0.1 wt% to 20 wt%.

[0042] In some embodiments, the CuO content is 0-15%, the CuO content is 0-15%, the CuS content is 0-15%, the CuI content is 0-20%, the CuSCN content is 0-15%, the CuGaO content is 0-15%, the CoO content is 0-8%, the CrO content is 0-15%, the SnO content is 0-15%, the SnS content is 0-15%, the HgO content is 0-15%, the PbO content is 0-15%, the AgO content is 0-15%, the AgO content is 0-15%, the MnO content is 0-10%, the PrO content is 0-15%, and the total content of the dopant is 0.1%-20%, based on the total mass of the nickel oxide-doped target.

[0043] According to a third aspect of the present application, there is further provided a use of a nickel oxide-doped target according to the first aspect of the present application or a nickel oxide-doped target produced by a method according to the second aspect of the present application in the manufacture of a hole transport layer of a perovskite solar cell.

[0044] Examples of the present application are described below. The examples described below are illustrative and are used only to interpret the present application, and should not be understood as limiting the present application. In the examples, specific techniques or conditions are not specified, but are carried out according to the techniques or conditions described in the technical literature or product instructions. Reagents or equipment used without a specified manufacturer are all common products that can be purchased commercially.

[0045] Example 1 (1) The back plate was fixed to a clamp of a plasma spraying device, and a 1.3 mm thick indium binding coating layer (binding material) was warm sprayed onto the back plate.

[0046] (2) Powdered nickel oxide substrate and dopant AgO were added into different plasma powder spray chambers of the plasma powder spray box, respectively, so as to add different materials independently.

[0047] The binding material of the back plate is heated to 200°C, and then the doping material and nickel oxide-based plasma powder are sprayed onto the heated binding material from the respective nozzles. The standard process parameters are: plasma power 15KW, angle 40°, back plate temperature room temperature to 200°C. The deposition and mixing on the back plate are performed to form a sandwich angle coating between the nozzles, creating a uniform doping effect. The spray amount of the corresponding nozzle is controlled to control the AgO doping amount to 0.5wt%. As the plasma spraying continued, the nickel oxide doped material on the back plate continued to thicken, and after the thickness reached a set value of 16 mm, the sprayer stopped the plasma spraying, yielding a nickel oxide target doped with AgO.

[0048] (3) The backplate target was removed and laser cut and dressed, the outer edge of the target was cut and salvaged, and the edge was dressed to form the target mounting edge, completing the basic secondary processing of the target, after which the target surface was cleaned.

[0049] Example 2 The other conditions were the same as in Example 1, except that the doping amount of AgO was adjusted to 1 wt %.

[0050] Example 3 The other conditions were the same as in Example 1, except that the doping amount of AgO was adjusted to 2 wt %.

[0051] Example 4 The procedure was the same as in Example 1, except that the doping material in step (2) was adjusted to CuI and the doping amount of CuI was controlled to 20 wt %.

[0052] Example 5 In step (2), the powdered nickel oxide substrate, CuGaO2 and SnS doping materials were added into three different plasma powder spray chambers of the plasma powder spray box, respectively, so that the different materials of nickel oxide substrate, CuGaO2 and SnS were added independently, and the doping amounts of CuGaO2 and SnS were controlled to 5 wt% respectively, which was the same as in Example 1.

[0053] Comparative Example 1 The target was a commercially available nickel oxide target.

[0054] Perovskite solar cell manufacturing Step 1: The ITO conductive glass substrate was cleaned and dried, and then subjected to UV light cleaning treatment to obtain the pre-treated substrate base.

[0055] Step 2: The pre-treated substrate base and the nickel oxide-doped target of Examples 1 to 5 or the nickel oxide target of Comparative Example 1 were transferred to a high-vacuum sputtering system, and a hole transport layer was sputtered onto the pre-treated substrate base under the following specific conditions:

[0056] Oxygen was used as the working gas, the gas flow rate was 200 sccm, and the sputtering pressure was 2.3 × 10 -3 A single layer of nickel oxide doped thin film with a thickness of 25 nm was sputter deposited as a hole transport layer under the conditions of 0.1 mbar, a target-to-substrate base distance of 79.5 mm, a sputtering power of 200 W, and a heating temperature of 125°C.

[0057] Step 3: The perovskite precursor solution was spin-coated onto the hole transport layer, and then chlorobenzene solvent was added and spin-coating was continued. After annealing at 100°C, a perovskite crystalline thin film, i.e., a light-absorbing layer, was obtained.

[0058] Step 4: A chlorobenzene solution of PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) was spin-coated onto the light-absorbing layer to form an electron-transporting layer.

[0059] Step 5: Under vacuum, a metal electrode material, a silver-aluminum alloy, was deposited on the electron transport layer by thermal evaporation to obtain a perovskite solar cell.

[0060] Testing method: Energy Band Distribution Test: The energy band distribution of the perovskite solar cell hole transport layer was tested by an X-ray photoelectron spectrometer (XPS) with model number Escalab 250Xi (from Thermo Scientific), thereby obtaining the valence band (CBM value), conduction band (VBM value) and energy band gap (ΔEg).

[0061] Spectral Response Test: The spectral curves of the perovskite solar cell hole transport layer were tested on a Thermo Scientific Nicole iS 50 infrared spectrophotometer.

[0062] The energy band distribution results of the hole transport layer of the perovskite solar cells manufactured using the nickel oxide-doped targets manufactured in Examples 1 to 3 of the present application and the nickel oxide target of Comparative Example 1 are shown in Table 1. The conversion efficiency results of the perovskite solar cells manufactured using the targets of each Example and Comparative Example are shown in Table 2.

[0063] The spectral curves of the hole transport layers of the perovskite solar cells produced using the targets of Example 1 and Comparative Example 1 are shown in FIG. 1. As can be seen from FIG. 1, the hole transport layers produced using the nickel oxide-doped target of the present application have higher transmittances for incident light of different wavelengths, indicating that the hole transport layers produced using the nickel oxide-doped target of the present application have higher spectral responses.

[0064] [Table 1]

[0065] [Table 2]

[0066] As can be seen from Table 1, the energy band gap of the hole transport layer produced using the nickel oxide doped targets of Examples 1 to 3 of the present application is narrower, indicating that the light absorption range of the hole transport layer of the present application is wider.

[0067] As can be seen from Table 2, the short-circuit current, short-circuit current density, and photoelectric conversion efficiency of the cell using the hole transport layer manufactured using the nickel oxide-doped target in each example of the present application are significantly improved. In particular, the photoelectric conversion efficiency of the co-doped hole transport layer is further improved, indicating that the electrical performance of the perovskite solar cell including the hole transport layer manufactured using the nickel oxide-doped target of the present application is significantly improved.

[0068] The above is only a preferred embodiment of the present application, and is not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. 1. A nickel oxide doped target comprising a nickel oxide base material and a doping material comprising at least one of Cu2O, Cu2S, CuI, CuSCN, CuGaO2, CoO, SnO, SnS, Hg2O, PbO, AgO, MnO, Pr2O3.

2. The dopant is Cu. ２ O, Cu ２ S, CuI, CuSCN, CuGaO ２ , CoO, SnO, SnS, Hg ２ O, PbO, AgO, MnO, Pr ２ O ３ The nickel oxide doped target of claim 1 , comprising at least two of:

3. 2. The nickel oxide-doped target according to claim 1, wherein the content of the dopant in the nickel oxide-doped target is 0.1 wt % to 20 wt %.

4. Cu based on the total mass of the nickel oxide doped target ２ The content of O is 0 to 15%, Cu ２ The content of S is 0 to 15%, the content of CuI is 0 to 20%, the content of CuSCN is 0 to 15%, CuGaO ２ The content of CoO is 0 to 8%, the content of SnO is 0 to 15%, the content of SnS is 0 to 15%, Hg ２ The content of O is 0 to 15%, the content of PbO is 0 to 15%, the content of AgO is 0 to 15%, the content of MnO is 0 to 10%, ２ O ３ 2. The nickel oxide doped target of claim 1, wherein the content of is 0-15%, and the total content of the doping materials is 0.1%-20%.

5. A method for producing a nickel oxide doped target, comprising: The method includes warm spraying a binding coating layer onto a target backplate or a target backpipe, introducing nickel oxide powder and powders of each dopant into respective plasma-generating spray coaters, and simultaneously plasma spraying the nickel oxide and each dopant onto the target backplate or the target backpipe to obtain the nickel oxide-doped target, wherein the dopant is selected from at least one of Cu2O, Cu2S, CuI, CuSCN, CuGaO2, CoO, SnO, SnS, Hg2O, PbO, AgO, MnO, and Pr2O3.

6. The dopant is Cu. ２ O, Cu ２ S, CuI, CuSCN, CuGaO ２ , CoO, SnO, SnS, Hg ２ O, PbO, AgO, MnO, Pr ２ O ３ 6. The method of claim 5, wherein the at least two of:

7. 6. The method of claim 5, wherein the content of the dopant in the nickel oxide doped target is 0.1 wt % to 20 wt %.

8. Cu based on the total mass of the nickel oxide doped target ２ The content of O is 0 to 15%, Cu ２ The content of S is 0 to 15%, the content of CuI is 0 to 20%, the content of CuSCN is 0 to 15%, CuGaO ２ The content of CoO is 0 to 8%, the content of SnO is 0 to 15%, the content of SnS is 0 to 15%, Hg ２ The content of O is 0 to 15%, the content of PbO is 0 to 15%, the content of AgO is 0 to 15%, the content of MnO is 0 to 10%, ２ O ３ 6. The method according to claim 5, wherein the content of is 0-15%, and the total content of the doping substances is 0.1%-20%.

9. A method for producing a hole transport layer for a perovskite solar cell, using the nickel oxide-doped target according to any one of claims 1 to 4.

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