Preparation method and application of laser ablation deposition anti-reflection light trapping film
By laser ablation of inorganic material targets, the deposition of anti-reflection light films on solar cells and LED substrates is solved, and the problems of high cost and complex process of traditional amplicon films are achieved, and the light absorption enhancement effect is achieved. It is suitable for a variety of substrate materials.
Patent Information
- Application Number
- CN202410244518.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-05
- Publication Date
- 2025-09-05
AI Technical Summary
The prior art has bottlenecks in improving the light absorption efficiency of solar cells and LEDs. Traditional amphipathic films are costly, complex processes and difficult to repeat. Plasma amphipathic technology has not been widely used, and traditional light trapping structures are not suitable for thin-filled batteries.
The laser ablation of inorganic material targets is used to directly deposit the anti-reflection light film on solar cells and LED substrates in one step. The anti-reflection light film is prepared on a variety of material targets using laser ablation technology, including infrared, visible, and ultraviolet lasers. The deposition time is completed within 20 minutes and is suitable for a variety of substrate materials.
It realizes low-cost and simple anti-reflection light film preparation, enhances the light absorption effect, improves the photoelectric conversion efficiency of solar cells and LEDs, and is suitable for large-scale production.
Smart Images
Figure CN120591731A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of anti-reflection and light-trapping film preparation, and in particular relates to a plasma anti-reflection and light-trapping film and a preparation method thereof. Background Art
[0002] Anti-reflection (AR) light-trapping films have a wide range of applications in optoelectronic devices such as solar cells and LEDs. Billions of dollars are invested annually to improve the electrical performance of solar cells. However, without significant technological breakthroughs, the absolute efficiency gains in recent years have not exceeded 0.5% per year. Therefore, improving optical light absorption and thus efficiency is an alternative approach, promising significant improvements in device efficiency. Traditional AR films used on encapsulating glass require wear resistance and cleaning and maintenance. The development of mainstream battery absorption layers, such as crystalline silicon pyramids and randomized surface light-trapping structures, also faces bottlenecks and limitations. Furthermore, as the thickness of crystalline silicon wafers used in mainstream battery technology decreases year by year, gradually approaching 100 microns or even lower, traditional pyramid structures and randomized surface light-trapping structures will become increasingly outdated. Plasma AR technology has not yet been applied in the photovoltaic and LED industries due to absorption losses in the metal itself, compound losses in contact with the semiconductor, complex processes, generally high costs, and poor repeatability. The present invention proposes a simple one-step method for directly depositing AR light-trapping films. This anti-reflection light-trapping film may produce plasma polarization effects, localized plasma resonance effects, and scattering effects, thereby improving light trapping and enhancing light absorption. It has great potential. Summary of the Invention
[0003] The purpose of the present invention is to provide an anti-reflective light-trapping film and a preparation method thereof. By adopting the technical solution of the present invention, an anti-reflective light-trapping film can be prepared, and the preparation method is simple, which is convenient for large-scale promotion and use.
[0004] In order to achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows: The present invention provides a method for preparing an anti-reflection light-trapping film, which adopts a method of laser ablation of an inorganic material target to directly deposit the anti-reflection light-trapping film on a solar cell or LED substrate in one step.
[0005] Furthermore, the method for preparing the anti-reflection light-trapping film is characterized in that the laser includes at least one of an infrared laser, a visible light laser, an ultraviolet laser, and a continuous laser and a pulsed laser.
[0006] Furthermore, the method for preparing the anti-reflection light-trapping film is characterized in that the substrate can be a solar cell, LED, chip, silicon wafer, glass, or plastic. Solar cells include all solar cells: silicon-based solar cells, perovskite solar cells, copper indium gallium tin solar cells, and cadmium telluride solar cells. The anti-reflection light-trapping film can be deposited at any step before solar cell packaging to achieve the light-trapping effect.
[0007] Furthermore, the method for preparing the anti-reflective light-trapping film is characterized in that the laser ablation target material can be carbon, silicon non-metal, or aluminum, nickel, titanium, vanadium, molybdenum, cobalt, iron, zinc, magnesium, chromium, indium, tin, bismuth, copper, niobium, zirconium, and alloys containing the above elements.
[0008] Furthermore, the method for preparing the anti-reflective light-trapping film is characterized in that the deposition must be completed within 20 minutes.
[0009] Furthermore, the method for preparing the anti-reflective light-trapping film is characterized in that the method can be carried out under atmospheric conditions or under vacuum conditions. When depositing under vacuum conditions, reactive oxygen can be introduced during the deposition process to produce an anti-reflective light-trapping film containing an oxide.
[0010] Furthermore, the method for preparing the anti-reflective light-trapping film is characterized in that the laser energy flux density is greater than 30 mJ / cm 2 The typical ablation process parameters of a fiber laser marking machine are as follows: laser power 30W, scanning speed 7.5m / s, scanning line spacing 0.05mm, and frequency 30KHz.
[0011] Furthermore, the preparation method of the anti-reflection light-trapping film is characterized in that the anti-reflection light-trapping film can be used on any layer before the solar cell packaging is completed, and may produce plasma polarization effect, local plasma resonance effect, and scattering effect, thereby enhancing light absorption; the anti-reflection light-trapping film can also be used for LEDs.
[0012] Furthermore, the anti-reflective light-trapping film prepared by the method for preparing the anti-reflective light-trapping film can be used on either the front or back surface, or on both surfaces simultaneously.
[0013] Furthermore, the anti-reflection light-trapping film can also be used in the fields of surface enhanced Raman lithography, photolithography, reactive ion etching, and nanoimprinting.
[0014] Furthermore, the anti-reflective light-trapping film prepared by any of the preparation methods described above and its application. Compared with the prior art, the advantages and beneficial effects of the present invention are: The preparation method of the present invention has low cost and can be deposited on solar cells, LEDs, chips, silicon wafers, glass, and plastic substrates to prepare anti-reflection and light-trapping films, and has the advantage of being scalable for production. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 These are typical scanning electron microscope (SEM) and energy dispersive X-ray spectrum of the vanadium-based anti-reflection light-trapping film prepared in Example 1.
[0016] Figure 2This is a diagram showing the anti-reflection and light-trapping effect of the vanadium-based anti-reflection and light-trapping film prepared in Example 1.
[0017] Figure 3 These are typical scanning electron microscope (SEM) and energy dispersive X-ray spectrum of the tungsten-based anti-reflection light-trapping film prepared in Example 2.
[0018] Figure 4 This is a diagram showing the anti-reflection and light-trapping effect of the tungsten-based anti-reflection and light-trapping film prepared in Example 2.
[0019] Figure 5 These are typical scanning electron microscope (SEM) and energy dispersive X-ray spectrum of the molybdenum-based anti-reflective light-trapping film prepared in Example 3.
[0020] Figure 6 This is a diagram showing the anti-reflection and light-trapping effect of the molybdenum-based anti-reflection and light-trapping film prepared in Example 3.
[0021] Figure 7 This is a diagram showing the anti-reflection and light-trapping effect of the 5-second bismuth-based anti-reflection and light-trapping film prepared in Example 4.
[0022] Figure 8 This is a diagram showing the anti-reflection and light-trapping effect of the 10-second bismuth-based anti-reflection and light-trapping film prepared in Example 4.
[0023] Figure 9 This is a diagram showing the anti-reflection and light-trapping effect of the silver-based anti-reflection and light-trapping film prepared in Example 5.
[0024] Figure 10 These are typical scanning electron microscope (SEM) and energy dispersive X-ray spectrum of the nickel-based anti-reflective light-trapping film prepared in Example 6.
[0025] Figure 11 This is a diagram showing the anti-reflection and light-trapping effect of the nickel-based anti-reflection and light-trapping film prepared in Example 6.
[0026] Figure 12 These are typical scanning electron microscope (SEM) and energy dispersive X-ray spectrum of the aluminum-based anti-reflective light-trapping film prepared in Example 7.
[0027] Figure 13 This is a typical anti-reflection and light-trapping effect diagram of the aluminum-based anti-reflection and light-trapping film prepared in Example 7.
[0028] Figure 14 This is a diagram showing the anti-reflection and light-trapping effect of the aluminum alloy anti-reflection and light-trapping film prepared in Example 8.
[0029] Figure 15 This is a diagram showing the anti-reflection and light-trapping effect of the 316 stainless steel anti-reflection and light-trapping film prepared in Example 9.
[0030] Figure 16 This is a diagram showing the anti-reflection and light-trapping effect of the 304 stainless steel anti-reflection and light-trapping film prepared in Example 10.
[0031] Figure 17 This is a diagram showing the anti-reflection and light-trapping effect of the zirconium-based anti-reflection and light-trapping film prepared in Example 11.
[0032] Figure 18 This is a diagram showing the anti-reflection and light-trapping effect of the magnesium alloy anti-reflection and light-trapping film prepared in Example 12.
[0033] Figure 19 This is a diagram showing the anti-reflection and light-trapping effect of the zinc-based anti-reflection and light-trapping film prepared in Example 13.
[0034] Figure 20 This is a diagram showing the anti-reflection and light-trapping effect of the iron-nickel alloy anti-reflection and light-trapping film prepared in Example 14. DETAILED DESCRIPTION
[0035] The following embodiments are provided to better illustrate the present invention, but the present invention is not limited to the following embodiments.
[0036] Vanadium-based anti-reflection and light-trapping films were deposited on silicon wafers by laser ablation of a vanadium target (99.99% purity). Half of the wafer was shielded by aluminum foil as a reference and no film was deposited, while the other half was unshielded and received anti-reflection film deposition: laser power 30W, scan speed 6.05, scan line spacing 0.03mm, frequency 30kHz, and deposition time 10s.
[0037] The anti-reflection light-trapping film prepared in Example 1 was observed by scanning electron microscope (SEM) and analyzed by EDS spectrum analysis. The results are as follows: Figure 1 The results show that the vanadium-based particles are evenly dispersed on the surface. Figure 2 . The wide spectrum anti-reflection is about 5.8%.
[0038] The crystalline silicon solar cells purchased were p-type silicon cells with an efficiency of 22.5%. Due to the need for testing, they were laser cut into small samples of 33*33mm. Some samples served as reference samples, while others were coated with a vanadium-based anti-reflection coating using the present invention. Under stable and consistent lighting conditions, the reference sample current was measured to be 38.23 mA / cm 2 , while the battery current of the anti-reflection light trapping film is 39.94 mA / cm 2 , confirming that the anti-reflection light-trapping effect is partially converted into current.
[0039] Tungsten-based anti-reflection light-trapping film was prepared by laser ablation of tungsten target (99.9% purity) on silicon wafer substrate: laser power was 30 W, scanning speed was 6.05, scanning line spacing was 0.03 mm, frequency was 30 kHz, and deposition time was 10 s.
[0040] The anti-reflection light-trapping film prepared in Example 2 was observed by scanning electron microscope (SEM) and analyzed by EDS spectrum analysis. The results are as follows: Figure 3 As shown in the figure, the results show that the tungsten-based particles are evenly dispersed on the surface. Figure 4 The wide spectrum anti-reflection is about 1.74%.
[0041] The tungsten-based anti-reflection film of this embodiment was deposited on an actual cell and compared with the current of the reference cell. Under stable and consistent lighting conditions, we measured the current of the reference sample to be 38.23 mA / cm 2 , while the battery current of the anti-reflection light trapping film is 38.89 mA / cm 2 , confirming that the anti-reflection light-trapping effect is partially converted into current.
[0042] Laser ablation of molybdenum targets (99.9% purity) was used to deposit molybdenum-based anti-reflection and light-trapping films on silicon wafer substrates. Half of the wafer was shielded by aluminum foil as a reference without any film deposition, while the other half was unshielded and received anti-reflection film deposition: laser power 30W, scanning speed 6.05, scanning line spacing 0.03mm, frequency 30kHz, and deposition time 10s.
[0043] The anti-reflection light-trapping film prepared in Example 3 was observed by scanning electron microscope (SEM) and analyzed by EDS spectrum analysis. The results are as follows: Figure 5 As shown in the figure, the results show that the molybdenum-based anti-reflection light-trapping film was successfully prepared. The main body of the film is molybdenum-based particles, which are evenly dispersed on the surface. Its anti-reflection light-trapping effect is shown in the figure. Figure 6 The wide spectrum anti-reflection is about 1.15%.
[0044] The molybdenum-based anti-reflection film of this embodiment was deposited on an actual cell and compared with the current of the reference cell. Under stable and consistent lighting conditions, we measured the current of the reference sample to be 38.23 mA / cm 2 , while the battery current of the anti-reflection light trapping film is 38.67 mA / cm 2 , confirming that the anti-reflection light-trapping effect is partially converted into current.
[0045] Bismuth target (99.9% purity) was laser ablated and deposited on both sides of silicon wafer substrate to prepare bismuth-based anti-reflection light-trapping film. Half of each side was shielded by aluminum foil as a reference without any film deposition, while the other half was unshielded and received anti-reflection film deposition: Two sets of process parameters were tried: laser power of 30W, scanning speed of 7.5, scanning line spacing of 0.05mm, frequency of 30KHz, and deposition time of 5s; laser power of 30W, scanning speed of 6.05, scanning line spacing of 0.03mm, frequency of 30KHz, and deposition time of 10s.
[0046] The anti-reflection and light-trapping film prepared in Example 4 was subjected to anti-reflection tests, and the anti-reflection and light-trapping effects on both sides are shown in FIG. Figure 7 、 Figure 8 The wide spectrum anti-reflection is about 6.8% and 1.5%.
[0047] The 10s bismuth-based anti-reflection film of this example was deposited on an actual cell and compared with the current of a reference cell. Under consistent lighting conditions, we measured the current of the reference sample to be 38.23 mA / cm 2 , while the battery current of the cell with anti-reflection light trapping film deposited is 38.63 mA / cm 2 , confirming that the anti-reflection light-trapping effect is partially converted into current.
[0048] Silver-based anti-reflection and light-trapping films were prepared by laser ablation of silver targets on silicon wafer substrates. Half of the same silicon wafer was shielded by aluminum foil as a reference without any film deposition, while the other half was unshielded and received anti-reflection film deposition: laser power was 30W, scanning speed was 6.05, scanning line spacing was 0.03mm, frequency was 30KHz, and deposition time was 10s.
[0049] The anti-reflection light-trapping film prepared in Example 4 was subjected to an anti-reflection test, and its anti-reflection light-trapping effect is shown in FIG. Figure 9 The wide spectrum anti-reflection is about 4.2%.
[0050] Nickel-based anti-reflection and light-trapping films were prepared by laser ablation of nickel target on silicon wafer substrate: laser power was 30 W, scanning speed was 6.05, scanning line spacing was 0.03 mm, frequency was 30 kHz, and deposition time was 10 s.
[0051] The anti-reflection light-trapping film prepared in Example 5 was observed by scanning electron microscope (SEM) and analyzed by EDS spectrum analysis. The results are as follows: Figure 10 As shown in the figure, the nickel-based particles are evenly dispersed on the surface. Figure 11 . Broad spectrum anti-reflection is about 0.45%.
[0052] Aluminum target was laser ablated and deposited on silicon wafer substrate to prepare aluminum-based anti-reflection light-trapping film: laser power was 30 W, scanning speed was 6.05, scanning line spacing was 0.03 mm, frequency was 30 kHz, and deposition time was 10 s.
[0053] The anti-reflection light-trapping film prepared in Example 6 was observed by scanning electron microscope (SEM) and analyzed by EDS spectrum analysis. The results are as follows: Figure 12 As shown in the figure, the results show that the aluminum-based anti-reflection light-trapping film was successfully prepared. The main body of the film is aluminum-based particles, which are evenly dispersed on the surface. Its anti-reflection light-trapping effect is shown in the figure. Figure 13 The wide spectrum anti-reflection is about 0.36%.
[0054] Laser ablation of aluminum alloy target was used to deposit aluminum-based alloy anti-reflection light-trapping film on silicon wafer substrate: laser power was 30W, scanning speed was 6.05, scanning line spacing was 0.03mm, frequency was 30KHz, and deposition time was 10s.
[0055] The anti-reflection light-trapping film prepared in Example 7 was subjected to an anti-reflection test, and its anti-reflection light-trapping effect is shown in FIG. Figure 14 . Broad spectrum anti-reflection is about 0.9%.
[0056] Laser ablation of 316 stainless steel target was used to deposit a 316 stainless steel-based light-reflection-reducing film on a silicon wafer substrate: the laser power was 30 W, the scanning speed was 6.05, the scanning line spacing was 0.03 mm, the frequency was 30 kHz, and the deposition time was 10 s.
[0057] The anti-reflection light-trapping film prepared in Example 8 was subjected to an anti-reflection test, and its anti-reflection light-trapping effect is shown in FIG. Figure 15 . Broad spectrum anti-reflection is about 2.2%.
[0058] Laser ablation of 304 stainless steel target was used to deposit a 304 stainless steel-based alloy anti-reflection light-trapping film on a silicon wafer substrate: the laser power was 30 W, the scanning speed was 6.05, the scanning line spacing was 0.03 mm, the frequency was 30 kHz, and the deposition time was 10 s.
[0059] The anti-reflection light-trapping film prepared in Example 9 was subjected to an anti-reflection test, and its anti-reflection light-trapping effect is shown in FIG. Figure 16 . Broad spectrum anti-reflection is about 0.9%.
[0060] A zirconium target was laser ablated and deposited on a silicon wafer substrate to prepare a zirconium-based anti-reflection light-trapping film. Half of the same silicon wafer was shielded by aluminum foil as a reference without any film deposition, while the other half was unshielded and received anti-reflection film deposition: laser power was 30W, scanning speed was 6.05, scanning line spacing was 0.03mm, frequency was 30KHz, and deposition time was 10s.
[0061] The anti-reflection light-trapping film prepared in Example 10 was subjected to an anti-reflection test, and its anti-reflection light-trapping effect is shown in FIG. Figure 17 . Broad spectrum anti-reflection is about 1.8%.
[0062] Magnesium alloy targets were laser ablated to deposit magnesium-based anti-reflection and light-trapping films on silicon wafer substrates. Half of the wafer was shielded by aluminum foil as a reference without any film deposition, while the other half was unshielded and received anti-reflection film deposition: laser power was 30W, scanning speed was 6.05, scanning line spacing was 0.03mm, frequency was 30KHz, and deposition time was 10s.
[0063] The anti-reflection light-trapping film prepared in Example 11 was subjected to an anti-reflection test, and its anti-reflection light-trapping effect is shown in FIG. Figure 18 . Broad spectrum anti-reflection is about 1.4%.
[0064] Laser ablation of zinc target was used to deposit zinc-based anti-reflection light-trapping film on silicon wafer substrate: laser power was 30 W, scanning speed was 6.05, scanning line spacing was 0.03 mm, frequency was 30 kHz, and deposition time was 10 s.
[0065] The anti-reflection light trapping film prepared in Example 12 was subjected to an anti-reflection light trapping test, and its anti-reflection light trapping effect is shown in FIG. Figure 19 . Broad spectrum anti-reflection is about 1.1%.
[0066] Laser ablation of iron-nickel alloy target was performed on silicon wafer substrate to deposit iron-nickel based alloy anti-reflection light trapping film: laser power was 30W, scanning speed was 6.05, scanning line spacing was 0.03mm, frequency was 30KHz, and deposition time was 10s.
[0067] The anti-reflection light-trapping film prepared in Example 13 was subjected to an anti-reflection test, and its anti-reflection light-trapping effect is shown in FIG. Figure 20 . Broad spectrum anti-reflection is about 0.1%. The above embodiments illustrate that the deposition rate and film composition can be adjusted by adjusting the speed, line spacing, power, frequency, etc. in the laser ablation target deposition process. Controlling these parameters can control the broad spectrum anti-reflection light trapping effect.
[0068] In addition, the anti-reflection light-trapping film can also be used in solar cells, LEDs, surface-enhanced Raman lithography, reactive ion etching, nanoimprinting and other fields.
[0069] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for a person skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to replace some of the technical features therein with equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions claimed to be protected by the present invention.
Claims
1. A method for preparing an anti-reflection light-trapping film by laser ablation deposition, characterized by: Laser equipment is used to ablate inorganic material targets, forming a plasma plume on their surface. The resulting particles will be deposited on solar cells and LEDs, forming an anti-reflection and light-trapping film on their surface.
2. The method for preparing an anti-reflective light-trapping film according to claim 1, wherein the laser comprises at least one of an infrared laser, a visible light laser, an ultraviolet laser, a continuous laser, and a pulsed laser.
3. The method for preparing an anti-reflection light-trapping film according to claim 1, wherein the substrate can be a solar cell, an LED, a chip, a silicon wafer, glass, or plastic. Solar cells include all solar cells: silicon-based solar cells, perovskite solar cells, copper indium gallium tin solar cells, and cadmium telluride solar cells.
4. According to the preparation method of the anti-reflective light-trapping film according to claim 1, the laser ablation target material can be carbon, silicon non-metal, or aluminum, nickel, titanium, vanadium, molybdenum, cobalt, iron, zinc, magnesium, chromium, indium, tin, bismuth, copper, niobium, zirconium, and alloys containing the above elements.
5. The method for preparing an anti-reflective light-trapping film according to claim 1 can be performed under atmospheric conditions or vacuum conditions. When depositing under vacuum conditions, reactive oxygen gas can be introduced during the deposition process to produce an anti-reflective light-trapping film containing an oxide.
6. The method for preparing the anti-reflective light-trapping film according to claim 1 is characterized in that the anti-reflective light-trapping film can be deposited on any layer before solar cells are packaged into modules to produce a light-trapping effect, thereby enhancing light absorption. The anti-reflective light-trapping film can be deposited on any layer before LEDs are packaged to produce a light-trapping effect, thereby enhancing light absorption.
7. The anti-reflective light-trapping film prepared by the method for preparing the anti-reflective light-trapping film according to claim 1 can be used on the front side, the back side, or both sides at the same time.
8. The method for preparing the anti-reflection light-trapping film according to claim 1 is characterized in that the anti-reflection light-trapping film can also be used in the fields of surface enhanced Raman lithography, photolithography, reactive ion etching, and nanoimprinting.
9. The anti-reflective light-trapping film prepared by the preparation method according to any one of claims 1 to 8 and its application.