Detection device and detection method

Abstract

This disclosure relates to a detection device and a detection method. The detection device includes: a transport line for transporting a substrate to be tested; a detection mechanism including a spectrometer, an anode assembly, and a cathode assembly. The anode assembly includes a gas flow path and an anode metal terminal having a reaction chamber. The gas flow path is connected to the reaction chamber for filling the reaction chamber with process gas or evacuating the reaction chamber. A first end of the anode metal terminal has a light-transmitting portion that closes the reaction chamber, and a second end opposite to the first end has an opening communicating with the reaction chamber. The anode assembly is connected to the spectrometer, and the light-transmitting portion is located between the detection port of the spectrometer and the reaction chamber. The cathode assembly includes an electrically connected cathode metal terminal and a power supply; and a driving mechanism for driving the anode metal terminal and the cathode metal terminal to move toward or away from the substrate to be tested located in the detection area. This detection device can realize online detection of the changes in spectral intensity / content of each element in the substrate to be tested over time / depth.

Description

Technical Field

[0001] This disclosure relates to the field of thin film composition detection technology, specifically to a detection device and detection method. Background Technology

[0002] The film structure of thin-film solar cells includes a back electrode layer, an absorber layer, a buffer layer, a window layer, and a top electrode layer. Among them, the absorber layer (copper indium gallium selenide, CIGS layer) is the key to determining the solar energy conversion efficiency. The content and vertical distribution of the four main elements copper, indium, gallium, and selenium in the absorber layer are direct factors affecting the solar energy conversion efficiency. Therefore, real-time detection of the composition is extremely important.

[0003] In related technologies, X-ray fluorescence spectrometry is used to test the content of each component (element) in the CIGS layer. However, this method only yields an average value at a certain depth, and the resulting percentage content is prone to deviation. Furthermore, this method only obtains the average content of each tested element within the surface, failing to capture the distribution of each element along the depth direction. In addition, offline component depth profiling not only prolongs the feedback time but also hinders timely process adjustments, thus impeding production efficiency. Summary of the Invention

[0004] The purpose of this disclosure is to provide a detection device and a detection method. The detection device can realize online detection of the changes in spectral intensity / content of each element in the substrate under test with time / depth, so as to facilitate timely judgment and adjustment of the process, which is beneficial to reduce manufacturing costs and improve production efficiency, thereby at least partially solving the above-mentioned technical problems.

[0005] To achieve the above objectives, a first aspect of this disclosure provides a detection apparatus, comprising:

[0006] A conveyor line for conveying a substrate to be tested and having a detection area and a detection space that runs vertically through the detection area;

[0007] The detection mechanism includes a spectrometer and an anode assembly located above the detection space, and a cathode assembly located below the detection space. The anode assembly includes a gas flow path and an anode metal terminal having a reaction chamber. The gas flow path communicates with the reaction chamber for filling the reaction chamber with process gas or evacuating the reaction chamber. A first end of the anode metal terminal has a light-transmitting portion that seals the reaction chamber, and a second end opposite the first end has an opening communicating with the reaction chamber. The anode assembly is connected to the spectrometer, and the light-transmitting portion is located between the spectrometer's detection port and the reaction chamber. The cathode assembly includes an electrically connected cathode metal terminal and a power supply.

[0008] A driving mechanism is used to drive the anode metal terminal and the cathode metal terminal to move toward or away from the substrate under test located in the detection area, so that the second end of the anode metal terminal can be attached to the upper surface of the substrate under test, and the cathode metal terminal can contact the lower surface of the substrate under test.

[0009] Optionally, the anode metal terminal is constructed as a cylindrical body, the reaction chamber is formed inside the cylindrical body, and the anode assembly further includes a first insulator arranged around the circumferential outer wall of the cylindrical body, with the gas flow path and the light-transmitting portion both disposed on the first insulator.

[0010] Optionally, the second end of the anode metal terminal protrudes from the bottom end of the first insulator and has a contact surface for adhering to the upper surface of the substrate under test.

[0011] Optionally, the anode metal terminal is constructed of any one of a copper ring, an aluminum ring, and a stainless steel ring, and / or the first insulator is constructed of a ceramic ring.

[0012] Optionally, a buffer cavity is provided between the outer peripheral wall of the anode metal terminal and the inner sidewall of the first insulator, and the anode metal terminal has at least one through hole connecting the buffer cavity and the reaction cavity, and the gas flow path is connected to the buffer cavity.

[0013] Optionally, the gas flow path includes a gas supply line and a gas extraction line. The gas supply line is connected to the reaction chamber for filling the reaction chamber with process gas, and the gas extraction line is connected to the reaction chamber for evacuating the reaction chamber.

[0014] Optionally, the light-transmitting part is constructed as an optical lens.

[0015] Optionally, the cathode assembly further includes a second insulator having an upward-opening mounting groove, in which the cathode metal terminal is disposed and its top protrudes beyond the top of the second insulator.

[0016] Optionally, the power supply is a DC power supply or a radio frequency power supply.

[0017] Optionally, the detection device further includes a controller and a position sensor. The position sensor is used to detect the position of the substrate under test relative to the conveyor line. The controller is connected to the position sensor, the conveyor line, the drive mechanism, the spectrometer, and the power signal, respectively.

[0018] Optionally, the conveyor line is a roller conveyor, which includes multiple conveyor rollers for conveying the substrate to be tested, and the detection space is the gap between any pair of adjacent conveyor rollers; or, the conveyor line includes at least two belt conveyors arranged in sequence, and the detection space is the gap between any pair of adjacent belt conveyors.

[0019] A second aspect of this disclosure provides a detection method applied to the detection apparatus described above, the detection method comprising:

[0020] The second end of the anode metal terminal is attached to the upper surface of the substrate to be tested located in the detection area, and the cathode metal terminal contacts the lower surface of the substrate to be tested;

[0021] The inside of the reaction chamber is evacuated and then filled with process gas.

[0022] Power is supplied to the cathode metal terminal;

[0023] The spectrometer identifies the characteristic spectra of each element in the reaction chamber and generates depth profile curves showing the changes in spectral intensity / content of each element over time / depth.

[0024] Optionally, the step of attaching the second end of the anode metal terminal to the upper surface of the substrate under test located in the detection area, and the cathode metal terminal contacting the lower surface of the substrate under test, includes:

[0025] The substrate to be tested is transported to the testing area via the conveyor line;

[0026] The driving mechanism drives the anode metal terminal and the cathode metal terminal to move toward the substrate under test, respectively.

[0027] Optionally, the step of evacuating the interior of the reaction chamber and then filling it with process gas includes:

[0028] The reaction chamber is evacuated through the gas extraction pipe of the gas flow path;

[0029] Process gas is introduced into the reaction chamber through the gas supply pipeline of the gas flow path, wherein the pressure inside the reaction chamber after the process gas is introduced is lower than the external atmospheric pressure.

[0030] Optionally, after identifying the characteristic spectra of each element in the reaction chamber using the spectrometer and generating depth profile curves showing the changes in spectral intensity / content of each element over time / depth, the detection method further includes:

[0031] When the spectral intensity / content of a set element in the substrate under test reaches a preset value, power supply to the cathode metal terminal is stopped after a delay of 2 to 10 seconds.

[0032] The anode metal terminal and the cathode metal terminal are respectively disconnected from the substrate under test.

[0033] The above-mentioned technical solution, namely the detection device provided in this disclosure, enables online detection of the changes in spectral intensity / content of each element in the substrate under test over time / depth, so as to facilitate timely judgment and adjustment of the process, which is beneficial to reduce manufacturing costs and improve production efficiency.

[0034] In the specific operation, after the substrate to be tested is transported to the testing area via the conveyor line, the drive mechanism drives the second end of the anode metal terminal of the anode assembly to contact the upper surface of the substrate, and drives the cathode metal terminal to contact the lower surface of the substrate. Then, the reaction chamber is evacuated through the gas flow path and filled with process gas, and power is supplied to the cathode metal terminal. Subsequently, the process gas in the reaction chamber forms plasma, i.e., a glow discharge is generated. The high-speed plasma reaches the upper surface of the substrate, causing the material on that surface to be sputtered out and diffuse into the glow discharge plasma, where it dissociates into atoms. The plasma is ionized and thus excited, causing the characteristic spectra of each element in the substrate to be emitted. The plasma glow of the ignition is then detected by a spectrometer. The plasma spectra at different wavelength peaks correspond to different elements. The spectrometer identifies the type of each element and quantifies the element content based on the spectral intensity. As the sputtering time increases, the change in the peak intensity corresponds to the change in the element content in the depth direction. As the ignition process continues, the spectral intensity / content of each element changes with time / depth, forming a depth profile curve, which allows for the detection of the changes in the spectral intensity / content of each element with time / depth.

[0035] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0036] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0037] Figure 1 This is a simplified structural diagram of the detection device provided in an exemplary embodiment of this disclosure;

[0038] Figure 2 This is a simplified schematic diagram of the structure of the anode assembly of the detection device provided in an exemplary embodiment of this disclosure;

[0039] Figure 3This is a simplified structural diagram of the cathode assembly of the detection device provided in an exemplary embodiment of this disclosure;

[0040] Figure 4 This is a simplified schematic diagram of the structure of the substrate under test provided in an exemplary embodiment of this disclosure;

[0041] Figure 5 This is a simplified schematic diagram of the system framework of the detection device provided in the exemplary embodiments of this disclosure;

[0042] Figure 6 This is a schematic diagram of the depth profile curve provided in an exemplary embodiment of this disclosure;

[0043] Figure 7 This is a schematic diagram of the depth profile curve provided in Exemplary Embodiment Two of this disclosure;

[0044] Figure 8 This is a flowchart of the detection method provided in an exemplary embodiment of this disclosure;

[0045] Figure 9 This is an implementation provided in the exemplary embodiments of this disclosure. Figure 8 Flowchart of step S100;

[0046] Figure 10 This is an implementation provided in the exemplary embodiments of this disclosure. Figure 8 Flowchart of step S200.

[0047] Explanation of reference numerals in the attached figures

[0048] 1-Conveyor line; 110-Roller conveyor; 111-Conveyor roller; 2-Substrate to be tested; 210-Substrate layer; 220-Back electrode layer; 230-Absorption layer; 240-Buffer layer; 3-Detection space; 4-Detection mechanism; 410-Spectrometer; 420-Anode assembly; 421-Gas flow path; 4211-Gas supply line; 4212-Gas extraction line; 422-Reaction chamber; 423-Anode metal terminal; 4231-Contact surface; 424-Light transmission part; 425-First insulator; 426-Buffer chamber; 427-Through hole; 430-Cathode assembly; 431-Cathode metal terminal; 432-Power supply; 433-Second insulator; 4331-Mounting groove; 5-Drive mechanism; 6-Controller; 7-Position sensor. Detailed Implementation

[0049] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.

[0050] In this disclosure, unless otherwise stated, directional terms such as "upper" and "lower" refer to the upper and lower positions within the space where the detection device is in use. Figure 1 The upper and lower directions in the drawing plane. "Inner" and "outer" refer to the inner and outer contours relative to the outline of the component or structure itself. Furthermore, it should be noted that terms such as "first" and "second" are used to distinguish one element from another and do not indicate sequence or importance. Additionally, in the description referring to the accompanying drawings, the same reference numerals in different drawings denote the same element.

[0051] The inventors discovered through research that in related technologies, X-ray fluorescence spectrometry is used to test the content of various components (elements) in the CIGS layer. Because X-rays penetrate to depths of several micrometers, they cannot achieve nanometer-level component analysis, thus failing to perform layer-by-layer peeling for in-depth analysis. The obtained content results are merely averages at a certain depth. For testing in the copper indium gallium selenide (CIGS) process, the primary X-rays penetrate the CIGS layer to reach the back electrode layer. Furthermore, for ultrathin CIGS layers, the X-rays not only penetrate the back electrode layer but also reach the substrate layer, causing the substrate composition to interfere with the test results. When normalizing the content results, this leads to deviations in the percentage content.

[0052] On the other hand, this method can only obtain the average content of each test element in the plane, and cannot obtain the distribution of each element in the depth direction. In particular, for CIGS layers prepared by the three-step co-evaporation method, it cannot determine the composition gradient of Ga element in the depth direction. Therefore, it cannot guide the three-step co-evaporation process and needs to be combined with online vertical depth analysis of composition.

[0053] Furthermore, related technologies typically employ offline methods to detect film composition, meaning that film composition cannot be detected during normal film production processes. This not only prolongs the feedback time and hinders timely process adjustments, thus impeding production efficiency, but also requires very small sample sizes for offline testing, necessitating the cutting of products on the production line, which compromises dimensional integrity. For rigid glass substrates, glass cutting is required, while for flexible substrates, roll-to-roll methods with lengths reaching up to one kilometer are used, making it impossible to sample and damage the substrate from the middle.

[0054] Based on this, the first aspect of this disclosure provides a detection device, with reference to Figures 1 to 5 As shown, the detection device includes a conveyor line 1, a detection mechanism 4, and a drive mechanism 5.

[0055] The conveyor line 1 is used to convey the substrate 2 to be tested and has a detection area and a detection space 3 that runs through the detection area in the vertical direction.

[0056] The detection mechanism 4 includes a spectrometer 410 and an anode assembly 420 located above the detection space 3, and a cathode assembly 430 located below the detection space 3. The anode assembly 420 includes a gas flow path 421 and an anode metal terminal 423 having a reaction chamber 422. The gas flow path 421 is connected to the reaction chamber 422 for filling the reaction chamber 422 with process gas or evacuating the reaction chamber 422. The first end of the anode metal terminal 423 is provided with a light-transmitting part 424 that closes the reaction chamber 422, and the second end opposite to the first end has an opening that communicates with the reaction chamber 422. The anode assembly 420 is connected to the spectrometer 410 and the light-transmitting part 424 is located between the detection port of the spectrometer 410 and the reaction chamber 422. The cathode assembly 430 includes an electrically connected cathode metal terminal 431 and a power supply 432.

[0057] The driving mechanism 5 is used to drive the anode metal terminal 423 and the cathode metal terminal 431 to move toward or away from the substrate 2 under test located in the detection area, so that the second end of the anode metal terminal 423 can be attached to the upper surface of the substrate 2 under test, and the cathode metal terminal 431 can contact the lower surface of the substrate 2 under test.

[0058] The above-mentioned technical solution, namely the detection device provided in this disclosure, enables online detection of the changes in spectral intensity / content of each element in the substrate 2 under test over time / depth, so as to facilitate timely judgment and adjustment of the process, which is beneficial to reduce manufacturing costs and improve production efficiency.

[0059] In the specific operation, after the substrate 2 to be tested is transported to the testing area by the conveyor line 1, the drive mechanism 5 drives the second end of the anode metal terminal 423 of the anode assembly 420 to adhere to the upper surface of the substrate 2, and drives the cathode metal terminal 431 to contact the lower surface of the substrate 2. Then, the reaction chamber 422 is evacuated through the gas flow path 421 and filled with process gas, and power is supplied to the cathode metal terminal 431 through the power supply 432 (wherein, the anode metal terminal 423 is grounded). Subsequently, the process gas in the reaction chamber 422 forms plasma, that is, a glow discharge is generated. After the high-speed plasma reaches the upper surface of the substrate 2, it sputters the material on the upper surface and propels it towards the surface. The glow discharge plasma diffuses and dissociates / atomizes within it, thus becoming excited and causing the characteristic spectra of each element in the substrate 2 to be emitted. The glow discharge plasma is then detected by a spectrometer 410. Different wavelength peaks in the plasma spectrum correspond to different elements. The spectrometer 410 identifies the type of each element and quantifies the element content based on the spectral intensity. As the sputtering time increases, the change in spectral peak intensity corresponds to the change in the element content in the depth direction. As the glow discharge process continues, the spectral intensity / content of each element changes with time / depth, forming a depth profile curve, which allows for the detection of the changes in the spectral intensity / content of each element with time / depth.

[0060] The substrate 2 under test can be any suitable thin film, and the detection device can detect the distribution of the film's components in the depth direction. For example, in one application scenario, the substrate 2 under test can be a combination of any number of layers in the film structure of a thin-film solar cell.

[0061] For example, refer to Figure 4 As shown, the substrate 2 under test may include a substrate layer 210, a back electrode layer 220, an absorber layer 230, and a buffer layer 240 stacked sequentially from bottom to top. The substrate layer 210 may be made of a metallic or non-metallic material; a metallic material may be, for example, stainless steel, and a non-metallic material may be, for example, glass. The back electrode layer 220 may be, for example, a Mo back electrode layer, i.e., using molybdenum (Mo) metal, and the thickness of the back electrode layer 220 may be, for example, 0.5 μm. The absorber layer 230 may be a CIGS layer, i.e., including four main elements: copper (Cu), indium (In), gallium (Ga), and selenium (Se), and the thickness of the absorber layer 230 may be, for example, 2–3 μm. The buffer layer 240 may be a CdS buffer layer, i.e., using cadmium sulfide (CdS) material, and the thickness of the buffer layer 240 may be, for example, 0.05 μm.

[0062] Real-time component detection not only focuses on the overall composition of the thin-film sampling area, but also requires attention to the distribution of gallium (Ga) along the depth direction of the CIGS layer for characterization and analysis of high-efficiency CIGS thin-film solar cells. This is because the V-shaped bandgap formed by the gradient distribution of Ga in the depth direction directly affects the cell efficiency. The V-shaped bandgap refers to the fact that the bandgap width of CIGS increases near the Mo back electrode layer and CdS buffer layer, while there is a minimum bandgap point within the CIGS layer. This corresponds to the Ga element's bandgap decreasing and then increasing along the depth direction of the CIGS layer, with the bandgap being higher near the interfaces of the Mo back electrode layer and CdS buffer layer than inside. Although this spatial V-shaped distribution of Ga can spontaneously form due to the different diffusion rates of In and Ga, the spontaneously formed V-shaped structure cannot form an ideal V-shaped bandgap, thus requiring subjective control. For the three-step co-evaporation method for preparing CIGS layers, gradually decreasing the evaporation rate of Ga in the first step and gradually increasing the deposition rate of Ga in the third step will change the gradient distribution of Ga. Therefore, this subjectively controlled process needs to be guided by the results of longitudinal depth profile analysis of the elemental distribution.

[0063] Therefore, using the detection device provided in this disclosure, when the substrate 2 to be tested includes a substrate layer 210, a back electrode layer 220, an absorption layer 230, and a buffer layer 240 arranged sequentially from bottom to top, the distribution of four elements—copper, indium, gallium, and selenium—in the absorption layer 230 along the depth direction can be detected, especially the distribution of gallium in the depth direction. For example, after the process gas generates a glow discharge, the generated high-speed plasma reaches the buffer layer 240, and the material of the buffer layer 240 is sputtered out. As the glow process or sputtering time continues, the sputtering etching depth gradually increases. After the four elements—copper, indium, gallium, and selenium—are sputtered out in the absorption layer 230, they are subsequently dissociated and atomized and excited, causing the characteristic spectra of the four elements to be emitted. After diffraction by the dispersive element in the spectrometer, light of different wavelengths is diffracted in different directions. The photosensitive element in the spectrometer identifies the type of each element and quantifies the element content based on the spectral intensity.

[0064] refer to Figure 6 and Figure 7 As shown, for each element, the intensity integral over a sputtering time is the content of that element in the material being tested. The vertical axis represents the content of each element, and the horizontal axis represents the etching depth, corresponding to the sputtering time. As the sputtering time increases, the etching depth gradually increases, passing through the buffer layer 240, the absorption layer 230, the back motor layer 220, and the substrate layer 210 from the surface to the interior. Thus, the depth profile curve of the substrate 2 under test is obtained.

[0065] In this way, the in-depth analysis curve can be used to guide and monitor the three-step process. On the one hand, at the beginning of the production line setup, the online detection results can guide the debugging of the three-step process, quickly establish a benchmark process, and reduce the time and cost of the debugging period. On the other hand, during stable production operation, the online detection results can be used to detect process stability, adjust the process in time if deviations occur, screen out unqualified products, and prevent unqualified products from flowing into the next process and wasting production costs.

[0066] Process gases include, but are not limited to, argon, helium, neon, and nitrogen.

[0067] The detection device provided in this disclosure can detect online changes in the intensity / content of each element in the substrate under test over time and depth. Online detection can be understood as the ability to promptly detect and provide feedback on changes in the content of each element in the depth direction, for example, within a CIGS layer, during the fabrication process of thin-film solar cells. For instance, after the substrate 2 under test undergoes CIGS co-evaporation deposition and CIGS coating, it exits the evaporation chamber and is transported to the detection area via conveyor line 1. In this detection area, changes in the content of each element in the depth direction within the CIGS layer are detected, providing timely feedback on the detection structure to guide the debugging of the three-step process. This avoids the problems associated with offline detection of thin-film composition in related technologies.

[0068] The conveyor line 1 can be, for example, a conveying mechanism on a thin-film solar cell production line. In some embodiments, the conveyor line 1 can be a roller conveyor 110, which includes multiple conveyor rollers 111 for conveying the substrate 2 to be tested. The detection space 3 is the gap between any pair of adjacent conveyor rollers 111, allowing the cathode metal terminal 431 to contact the lower surface of the substrate 2. The roller conveyor 110 not only facilitates the transfer of thin-film solar cells in various processes but also allows for the pre-setting of detection areas to detect changes in the elemental content of any layer in the film structure of the thin-film solar cell along the depth direction during a specific process.

[0069] In other embodiments, the conveyor line 1 may further include at least two belt conveyors arranged sequentially, and the detection space 3 is the gap between any pair of adjacent belt conveyors, which allows the cathode metal terminal 431 to contact the lower surface of the substrate 2 under test. This disclosure is not limited thereto.

[0070] In some implementations, reference Figure 5 As shown, the detection device may further include a controller 6 and a position sensor 7. The position sensor 7 is used to detect the position of the substrate 2 under test relative to the conveyor line 1. The controller 6 is connected to the position sensor 7, the conveyor line 1, the drive mechanism 5, the spectrometer 410, and the power supply 432. When the position sensor 7 detects that the substrate 2 under test has been conveyed to the detection area, it feeds back a detection signal to the controller 6. After receiving the detection signal, the controller 6 can control the conveyor line 1 to stop operating, keeping the substrate 2 under test in the detection area, and simultaneously control the drive mechanism 5 to move the cathode metal terminal 431 and the anode metal terminal 423 toward the substrate 2 under test. In addition, the controller 6 can also control the power supply 432 to provide power to the cathode metal terminal 431 and to turn on the spectrometer 410. The controller 6 can be, for example, a PLC controller or a microcontroller, etc., and this disclosure does not specifically limit it.

[0071] The position sensor 7 can be located downstream of the conveyor line 1 in the detection area. This allows the position sensor 7 to detect the edge of the substrate 2 under test and then send a detection signal back to the controller 6. Consequently, the detection position of the substrate 2 under test is located at its edge, which is the dead zone that will be cleared in subsequent processes, thus reducing detection costs. The position sensor 7 can be any suitable sensor, such as a proximity sensor positioned above the conveyor line 1; this disclosure does not impose any specific limitation.

[0072] In some implementations, reference Figure 2 As shown, the anode metal terminal 423 is constructed as a cylindrical body, and the reaction chamber 422 is formed inside the cylindrical body. The anode assembly 420 also includes a first insulator 425 arranged around the circumferential outer wall of the cylindrical body. The gas flow path 421 and the light-transmitting part 424 are both disposed on the first insulator 425. By arranging the first insulator 425, protection can be provided for the anode metal terminal, as well as insulation protection, while facilitating the installation of the gas flow path 421 and the light-transmitting part 424.

[0073] In addition, the second end of the anode metal terminal 423 protrudes from the bottom end of the first insulator 425 to facilitate full contact with the upper surface of the substrate 2 under test. The anode metal terminal 423 has a contact surface 4231 for adhering to the upper surface of the substrate 2 under test. Through the contact between surfaces, the contact area can be increased, while ensuring the airtight contact between the anode metal terminal 423 and the substrate 2 under test, thus ensuring the airtightness of the reaction chamber 422.

[0074] In some specific embodiments, the anode metal terminal 423 can be constructed as any one of a copper ring, an aluminum ring, and a stainless steel ring. Taking a copper ring as an example, the inner diameter of the copper ring ranges from φ2 to 10 mm, for example, it can be 4 mm. In addition, the anode metal terminal 423 can also be constructed as other conductive metal materials, etc., and this disclosure does not specifically limit it in this regard.

[0075] Furthermore, the first insulator 425 may be constructed as, for example, a ceramic ring, or other materials with insulating properties, and this disclosure does not specifically limit it in this regard.

[0076] The bottom end of the first insulator 425 may be provided with a groove for mounting the light-transmitting part 424. The bottom surface of the groove is connected to the reaction chamber 422. An annular sealing ring or the like may be provided between the light-transmitting part 424 and the groove to enhance the sealing effect.

[0077] Furthermore, the light-transmitting portion 424 can be, for example, an optical lens, such as a convex lens or a plane mirror, and this disclosure does not specifically limit it in this regard.

[0078] In some specific embodiments, a buffer cavity 426 is provided between the outer peripheral wall of the anode metal terminal 423 and the inner sidewall of the first insulator 425. The anode metal terminal 423 has at least one through hole 427 connecting the buffer cavity 426 and the reaction chamber 422. A gas flow path 421 is connected to the buffer cavity 426 to fill the reaction chamber 422 with process gas through the gas flow path 421, thereby providing a buffer space and preventing direct gas flow. The radial gap between the outer peripheral wall of the anode metal terminal 423 and the inner sidewall of the first insulator 425 can be, for example, 1 mm.

[0079] In some specific implementation methods, refer to Figure 2 As shown, the gas flow path 421 includes a gas supply pipe 4211 and a gas extraction pipe 4212. The gas supply pipe 4211 is connected to the reaction chamber 422 to introduce process gas into the reaction chamber 422, and the gas extraction pipe 4212 is connected to the reaction chamber 422 to evacuate the reaction chamber 422. Thus, after evacuating the reaction chamber 422 through the gas extraction pipe 4212, the anode metal terminal 423 can be negatively adsorbed onto the upper surface of the substrate 2 under test, ensuring the airtightness of the reaction chamber 422. Subsequently, process gas can be introduced into the reaction chamber 422 through the gas supply pipe 4211. The pressure inside the reaction chamber 422 after filling with process gas is lower than the external atmospheric pressure, ensuring the negative pressure adsorption effect between the anode metal terminal 423 and the substrate 2 under test. For example, the pressure range inside the reaction chamber 422 after filling with process gas can be 50 to 1000 Pa, for example, 500 Pa, in order to maintain a good negative pressure adsorption effect and ensure the ignition process inside the reaction chamber 422.

[0080] Furthermore, the evacuation line 4212 can be connected to a vacuum generator to evacuate the reaction chamber 422. A first solenoid valve, etc., connected to the controller 6, can also be installed on the evacuation line 4212 to control the opening and closing of the line. The gas supply line 4211 can be connected to a pressure tank storing process gas. A second solenoid valve, etc., connected to the controller 6, can also be installed on the gas supply line 4211 to control the opening and closing of the line. Additionally, a pressure gauge can be installed on the line between the second solenoid valve and the reaction chamber 422 to monitor the gas pressure inside the reaction chamber 422 in real time.

[0081] In some implementations, reference Figure 3 As shown, the cathode assembly 430 also includes a second insulator 433, which has an upward-opening mounting groove 4331. The cathode metal terminal 431 is disposed in the mounting groove 4331 and its top protrudes from the top of the second insulator 433. By arranging the second insulator 433, protection against electric shock and short circuits can be provided to the cathode terminal.

[0082] In some embodiments, depending on the material of the substrate layer 210, the power supply 432 can be a DC power supply or a radio frequency power supply.

[0083] For example, when the substrate layer 210 is made of non-metallic materials such as glass, the power supply 432 can be an RF power supply with a frequency of 300 to 5000 Hz, for example, 3000 Hz, and an execution cycle, i.e., a working cycle of 0.2 to 1, for example, 0.375.

[0084] When the substrate layer 210 is made of stainless steel or other metal materials, the power supply 432 can be a DC power supply with a power of 5 to 100W, for example, 30W.

[0085] The driving mechanism 5 may include a first driving mechanism for moving the anode metal terminal 423 and a second driving mechanism for moving the cathode metal terminal 431. The first driving mechanism may include, for example, a cylinder, an electric push rod, or other linear driving mechanisms, or even a robotic arm. Its purpose is simply to enable the anode metal terminal 423 to move closer to or away from the substrate 2 under test. This disclosure does not specifically limit its use. The second driving mechanism may also be a cylinder, an electric push rod, or other linear driving mechanisms. Its purpose is simply to enable the cathode metal terminal 431 to move closer to or away from the substrate 2 under test. This disclosure does not specifically limit its use.

[0086] Based on the aforementioned detection apparatus, a second aspect of this disclosure provides a detection method applied to the aforementioned detection apparatus, with reference to... Figure 8 As shown, the detection method includes the following steps:

[0087] In step S100, the second end of the anode metal terminal 423 is attached to the upper surface of the substrate 2 to be tested located in the detection area, and the cathode metal terminal 431 contacts the lower surface of the substrate 2 to be tested.

[0088] Step S200: After evacuating the inside of the reaction chamber 422, process gas is introduced.

[0089] Step S300: Power is supplied to the cathode metal terminal 431;

[0090] In step S400, the characteristic spectra of each element in the reaction chamber 422 are identified by the spectrometer 410, and depth profile curves of the spectral intensity / content of each element as a function of time / depth are generated.

[0091] Through the above technical solution, after the power supply 432 supplies power to the cathode metal terminal 431, the process gas in the reaction chamber 422 forms plasma. After the high-speed plasma reaches the upper surface of the substrate 2 under test, the material on the upper surface is sputtered out and diffuses into the glow discharge plasma, where it is dissociated and atomized, thereby being excited. As the sputtering time continues, the etching depth gradually increases, and then each element in the substrate 2 under test is sputtered out. The type of each element is identified and the element content is quantified by a spectrometer, thereby obtaining the depth profile curve of the spectral intensity / content of each element as a function of time / depth.

[0092] In some implementations, step S100 can be achieved in the following ways:

[0093] Step S101: The substrate 2 to be tested is transported to the detection area by the conveyor line 1. The position of the substrate 2 to be tested relative to the conveyor line 1 can be detected by the position sensor 7. When the substrate 2 to be tested moves to the detection area, a detection signal is fed back to the controller 6 to stop the operation of the conveyor line 1.

[0094] In step S102, the anode metal terminal 423 and the cathode metal terminal 431 are driven by the driving mechanism 5 to move toward the substrate 2 under test, so that the second end of the anode metal terminal 423 is attached to the upper surface of the substrate 2 under test, and the cathode metal terminal 431 contacts the lower surface of the substrate 2 under test.

[0095] In some implementations, step S200 can be achieved in the following ways:

[0096] In step S201, the reaction chamber 422 is evacuated through the gas extraction pipe 4212 of the gas flow path 421 so that the anode metal terminal 423 is negatively pressure adsorbed to the upper surface of the substrate 2 under test, thus ensuring the airtightness of the reaction chamber 422.

[0097] In step 202, process gas is introduced into the reaction chamber 422 through the gas supply pipe 4211 of the gas flow path 421. The pressure inside the reaction chamber 422 after the process gas is introduced is lower than the external atmospheric pressure to ensure that the anode metal terminal 423 can still maintain negative pressure adsorption with the substrate 2 under test after the process gas is introduced. The pressure inside the reaction chamber 422 after the process gas is introduced can be, for example, 500 Pa or 750 Pa.

[0098] In some embodiments, after step S400, the detection method further includes:

[0099] Step S500: When the spectral intensity / content of the set element in the substrate 2 to be tested reaches the preset value, power supply to the cathode metal terminal 431 is stopped after a delay of 2 to 10 seconds.

[0100] In this case, the substrate 2 under test includes a substrate layer 210, a back electrode layer 220, an absorption layer 230 and a buffer layer 240 arranged sequentially from bottom to top. The set element can be, for example, copper, and the preset value can be 0. For example, when the content or spectral intensity of copper reaches 0, it indicates that the etching depth is close to the junction of the CIGS layer and the Mo back electrode layer. After a delay of 2 to 10, the power supply to the cathode metal terminal 431 can be stopped, which indicates that the detection process is complete.

[0101] In step S600, the anode metal terminal 423 and the cathode metal terminal 431 are respectively disconnected from the substrate 2 under test. This test is now complete, and the above steps can be repeated for the next test.

[0102] This disclosure exemplarily describes embodiments of two testing methods when the substrate layer 210 of the substrate 2 under test is glass or stainless steel.

[0103] In Embodiment 1, the substrate layer 210 is made of glass, wherein:

[0104] The substrate layer 210 is 3mm float glass. Before reaching the detection device, it undergoes substrate cleaning, back electrode deposition, and CIGS co-evaporation deposition. When the CIGS coating exits the co-evaporation chamber and is transported to the detection area via the transport line 1, the transport is stopped.

[0105] Driven by the drive mechanism 5, the second end of the anode metal terminal 423 is made to adhere to the upper surface of the substrate 2 under test, and the cathode metal terminal 431 is made to contact the lower surface of the substrate 2 under test.

[0106] The reaction chamber 422 is evacuated through the vacuum pipe 4212, so that the anode metal terminal 423 is attracted to the upper surface of the substrate 2 to be tested.

[0107] Process gas, such as argon, is introduced into the reaction chamber 422 through the gas supply line 4211 at a pressure of 500 Pa.

[0108] Ignition is achieved by supplying power to the cathode metal terminal 431 via an RF power supply, with a power of 30W, a frequency of 3000Hz, and an execution cycle of 0.375.

[0109] Plasma glow discharge spectra are acquired using a spectrometer, and element types are automatically identified based on pre-stored spectral peak positions in a database. Element content is quantified by spectral intensity. As the glow discharge process continues, the spectral intensity / content of each detected element changes with time / depth, forming a depth profile curve. This depth profile curve can be referenced... Figure 6 The depth profile curve is shown as an example.

[0110] In Example 2, the substrate layer 210 is made of stainless steel, wherein:

[0111] The stainless steel is 30μm thick and of grade ASTM430. Before reaching the testing device, it undergoes roll-to-roll substrate cleaning, barrier layer deposition, back film and back electrode deposition, and CIGS co-evaporation deposition. After the CIGS coating is applied, it exits the co-evaporation chamber and is transported to the testing area via conveyor line 1, after which the transport stops.

[0112] Driven by the drive mechanism 5, the second end of the anode metal terminal 423 is made to adhere to the upper surface of the substrate 2 under test, and the cathode metal terminal 431 is made to contact the lower surface of the substrate 2 under test.

[0113] The reaction chamber 422 is evacuated through the vacuum pipe 4212, so that the anode metal terminal 423 is attracted to the upper surface of the substrate 2 to be tested.

[0114] Process gas, such as argon, is introduced into the reaction chamber through gas supply line 4211 at a pressure of 750 Pa.

[0115] Ignition is achieved by supplying power to the cathode metal terminal 431 via a DC power supply, with a power of 17W, a pulse frequency of 3500Hz, and an execution cycle of 0.5.

[0116] Plasma glow discharge spectra are acquired using a spectrometer, and element types are automatically identified based on pre-stored spectral peak positions in a database. Element content is quantified by spectral intensity. As the glow discharge process continues, the spectral intensity / content of each detected element changes with time / depth, forming a depth profile curve. This depth profile curve can be used as a reference. Figure 7 The depth profile curve is shown as an example in the figure;

[0117] When the spectral intensity of copper drops to 0, the spectrum acquisition stops after a 2-second delay. The anode metal terminal 423 moves upward away from the upper surface of the substrate 2 under test, and the cathode metal terminal 431 moves downward away from the lower surface of the substrate 2 under test.

[0118] The transmission step of the substrate under test 2 stops at 100mm, and the next test is performed. The above steps are repeated.

[0119] Depend on Figure 7 As can be seen, the CIGS layer is approximately 2 μm thick. At the interface, the signal intensities of copper, indium, gallium, and selenium decrease, while the molybdenum signal intensity increases, indicating that this is the boundary between the CIGS layer and the Mo back electrode layer. Inside the CIGS layer, the gallium content first decreases and then increases with increasing depth, reaching a minimum near 0.3 μm. Correspondingly, the indium content first increases and then decreases.

[0120] In Example 1, the depth distribution curve of gallium is relatively flat, while in Example 2, gallium exhibits a gradient distribution along the depth direction. This difference stems from the different process methods. Example 1 uses a one-step co-evaporation method to prepare CIGS, while Example 2 uses a three-step co-evaporation method. The detection device provided in this disclosure can detect the gradient distribution curve of gallium in the three-step co-evaporation method, distinguishing the depth location of the lowest point in the gradient distribution and the gradient slopes on both sides. This is crucial for guiding and monitoring the three-step co-evaporation process.

[0121] The preferred embodiments of this disclosure have been described in detail above with reference to the accompanying drawings. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0122] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0123] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A detection device, characterized in that, include: A conveyor line for conveying a substrate to be tested and having a detection area and a detection space that runs vertically through the detection area, wherein the substrate to be tested is a thin film; The detection mechanism includes a spectrometer and an anode assembly located above the detection space, and a cathode assembly located below the detection space. The anode assembly includes a gas flow path and an anode metal terminal having a reaction chamber. The gas flow path is connected to the reaction chamber for filling the reaction chamber with process gas or evacuating the reaction chamber. A first end of the anode metal terminal is provided with a light-transmitting portion that closes the reaction chamber, and a second end opposite to the first end has an opening that communicates with the reaction chamber. The anode assembly is connected to the spectrometer, and the light-transmitting portion is located between the detection port of the spectrometer and the reaction chamber. The cathode assembly includes an electrically connected cathode metal terminal and a power supply, wherein the power supply is a radio frequency power supply. The anode metal terminal is constructed as a cylindrical body, the reaction chamber is formed inside the cylindrical body, and the anode assembly further includes a first insulator arranged around the circumferential outer wall of the cylindrical body. The gas flow path and the light-transmitting portion are both disposed on the first insulator. The second end of the anode metal terminal protrudes from the bottom end of the first insulator and has a contact surface for adhering to the upper surface of the substrate under test. A driving mechanism is used to drive the anode metal terminal and the cathode metal terminal to move toward or away from the substrate under test located in the detection area, so that the second end of the anode metal terminal can be attached to the upper surface of the substrate under test, and the cathode metal terminal can contact the lower surface of the substrate under test.

2. The detection device of claim 1, wherein, The anode metal terminal is constructed of any one of a copper ring, an aluminum ring, and a stainless steel ring, and / or the first insulator is constructed of a ceramic ring.

3. The detection device of claim 1, wherein, A buffer cavity is provided between the outer peripheral wall of the anode metal terminal and the inner sidewall of the first insulator. The anode metal terminal has at least one through hole connecting the buffer cavity and the reaction cavity, and the gas flow path is connected to the buffer cavity.

4. The detection device according to claim 1 or 3, characterized in that The gas flow path includes a gas supply line and a gas extraction line. The gas supply line is connected to the reaction chamber for filling the reaction chamber with process gas, and the gas extraction line is connected to the reaction chamber for evacuating the reaction chamber.

5. The detection device of claim 1, wherein, The light-transmitting part is constructed as an optical lens.

6. The detection device of claim 1, wherein, The cathode assembly further includes a second insulator having an upward-opening mounting groove, in which the cathode metal terminal is disposed and its top protrudes beyond the top of the second insulator.

7. The detection device of claim 1, wherein, The detection device further includes a controller and a position sensor. The position sensor is used to detect the position of the substrate under test relative to the conveyor line. The controller is connected to the position sensor, the conveyor line, the drive mechanism, the spectrometer, and the power signal, respectively.

8. The detection device of claim 1, wherein, The conveyor line is a roller conveyor, which includes multiple conveyor rollers for conveying the substrate to be tested. The detection space is the gap between any pair of adjacent conveyor rollers; or... The conveyor line includes at least two belt conveyors arranged in sequence, and the detection space is the gap between any pair of adjacent belt conveyors.

9. A method of detection, characterized in that The detection method, applied to the detection apparatus according to any one of claims 1-8, comprises: The second end of the anode metal terminal is attached to the upper surface of the substrate to be tested located in the detection area, and the cathode metal terminal contacts the lower surface of the substrate to be tested; The inside of the reaction chamber is evacuated and then filled with process gas. Power is supplied to the cathode metal terminal; The spectrometer identifies the characteristic spectra of each element in the reaction chamber and generates depth profile curves showing the changes in spectral intensity / content of each element over time / depth.

10. The detection method according to claim 9, characterized in that, The step of attaching the second end of the anode metal terminal to the upper surface of the substrate under test located in the detection area, and the cathode metal terminal contacting the lower surface of the substrate under test, includes: The substrate to be tested is transported to the testing area via the conveyor line; The driving mechanism drives the anode metal terminal and the cathode metal terminal to move toward the substrate under test, respectively.

11. The detection method according to claim 9, characterized in that, The process of evacuating the interior of the reaction chamber and then filling it with process gas includes: The reaction chamber is evacuated through the gas extraction pipe of the gas flow path; Process gas is introduced into the reaction chamber through the gas supply pipeline of the gas flow path, wherein the pressure inside the reaction chamber after the process gas is introduced is lower than the external atmospheric pressure.

12. The detection method of claim 9, wherein, After identifying the characteristic spectra of each element within the reaction chamber using the spectrometer and generating depth profile curves showing the changes in spectral intensity / content of each element over time / depth, the detection method further includes: When the spectral intensity / content of a set element in the substrate under test reaches a preset value, power supply to the cathode metal terminal is stopped after a delay of 2 to 10 seconds. The anode metal terminal and the cathode metal terminal are respectively disconnected from the substrate under test.

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