CN110885972A - ALD preparation method for eliminating dot defects of camera module and product thereof - Google Patents
ALD preparation method for eliminating dot defects of camera module and product thereof Download PDFInfo
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- CN110885972A CN110885972A CN201911060808.8A CN201911060808A CN110885972A CN 110885972 A CN110885972 A CN 110885972A CN 201911060808 A CN201911060808 A CN 201911060808A CN 110885972 A CN110885972 A CN 110885972A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
Abstract
The invention provides an ALD preparation method for eliminating the dot defect of a camera module and a product thereof, wherein the ALD is used for realizing the alternate deposition of high-refractive-index film layers and low-refractive-index film layers of an optical element, reaction materials are adsorbed and deposited on a substrate base plate in a reaction cavity in a gas form, no evaporation or sputtering process exists, and the source of the dot defect is eliminated, so that the dot defect of large particles can not be formed, the imaging quality of the camera module is greatly improved, and the ALD is applied to the processing process of the camera module with practical operation significance.
Description
Technical Field
The invention relates to the technical field of camera modules, in particular to an ALD (atomic layer deposition) preparation method for eliminating dot defects of a camera module and a product thereof.
Background
Along with the continuous improvement of industries such as intelligent terminal, on-vehicle, scanner, smart mobile phone, projecting apparatus, security protection control to high definition camera shooting requirement to and the extensive application of augmented reality, 3D technique and gesture recognition technique in artificial intelligence field, optical lens and the module industry of making a video recording also continuously carry out the innovation iteration of technique when developing at a high speed, in order to satisfy new application requirement.
Dots are a type of defect occurring in optical lenses and image pickup modules, and refer to dot-like protrusions, sometimes called particles (particles), formed on the surface of a substrate. The dots are mainly formed by the fact that in the current optical coating process (namely, vacuum thermal evaporation and magnetron sputtering), large-particle film material dots are inevitably formed along with film material vapor or sputtering particles deposited on the surface of a substrate. Sometimes individual dots, and in severe cases, fragmented fine dots, and large particles can even damage the substrate surface and can severely affect imaging performance. Therefore, most manufacturers currently require that the dots in the optical element not exceed 5 μm in order to ensure the imaging effect.
However, almost all optical components are coated with various films to achieve specific optical properties, i.e. the process of coating one or more layers of metal or dielectric films on the surface of the optical component is used to reduce or increase the reflection, beam splitting, color separation, filtering, polarization, etc. of light; the optical coating process mainly adopts vacuum thermal evaporation (evaporation) and magnetron sputtering, and no effective means for controlling or reducing dots exists.
The vacuum thermal evaporation is to heat the evaporation substance to evaporate and deposit the evaporation substance on the surface of the substrate to form a solid film under the vacuum condition, and the process is as follows: (1) various heat energy conversion modes (such as resistance heating, electronic heating, high-frequency induction heating, electric arc heating, laser heating and the like) are adopted to evaporate or sublimate the coating material particles to form gaseous particles with certain energy; (2) the gaseous particles are transported to the matrix by a substantially collision-free linear motion; (3) the particles are deposited on the surface of the substrate and coalesced into a film; (4) the atoms constituting the thin film are rearranged or chemically bonded. Since heating and condensation processes cannot be absolutely uniform, large droplets or large particles inevitably occur, so that the point defects in the optical coating film cannot be effectively controlled, and points with a particle size of more than 5 μm are very likely to occur, which is an important factor influencing the yield at present.
Magnetron sputtering is a technology for bombarding the surface of a target by using charged particles in vacuum to deposit the bombarded particles on a substrate, and the process is as follows: (1) the electrons collide with argon atoms in the process of flying to the substrate under the action of the electric field E, so that the argon atoms are ionized to generate Ar positive ions and new electrons, (2) the new electrons fly to the substrate, and the Ar ions accelerate to fly to a cathode target under the action of the electric field and bombard the surface of the target at high energy, so that the target is sputtered; (3) in the sputtered particles, neutral target atoms or molecules are deposited on the substrate to form a thin film. Similarly, during the bombardment of the target material, there is a high possibility that large particles are generated and deposited on the substrate to form dots, which cannot be effectively controlled.
Therefore, in the industrial production of the optical lens and the camera module, an effective control way for controlling the generation and the number of the point defects is lacked, the qualification rate of products is reduced, the production cost is increased, and a more optimized production process needs to be developed. .
Disclosure of Invention
One objective of the present invention is to provide an ALD method for eliminating dot defects of a camera module, which can fundamentally solve the generation path of dots and does not generate dot defects with a particle size of micrometer.
The second object of the present invention is to provide a product obtained by the above production method, which can greatly reduce defects caused by point defects.
In order to achieve the purpose, the invention provides one of the following technical schemes:
an ALD preparation method for eliminating dot defects of a camera module is characterized by comprising the following steps:
s1, placing a substrate base plate in the reaction cavity, and heating to 100-400 ℃;
s2: introducing a first reaction precursor into the atomic layer reaction cavity, and chemically adsorbing the first reaction precursor on the substrate to form a first film layer;
s3: pumping out excess first reaction precursor and purging with inert gas;
s4: introducing a second reaction precursor into the reaction cavity, and reacting with the first reaction precursor chemically adsorbed on the surface of the substrate base plate to form a first refractive index layer;
s5: pumping excess second reaction precursor and reaction by-products out and purging with an inert gas;
s6: introducing a third reaction precursor into the reaction cavity, and chemically adsorbing the third reaction precursor on the surface of the first refractive index layer to form a second film layer;
s7: pumping out excess third reaction precursor and purging with inert gas;
s8: introducing a fourth reaction precursor into the atomic layer reaction cavity, and reacting with a third reaction precursor chemically adsorbed on the surface of the first refractive index layer to form a second refractive index layer; the refractive index of the second refractive index layer > the refractive index of the first refractive index layer;
s9: excess fourth reaction precursor and reaction by-products are pumped out.
Further, the preparation method also comprises the step of forming an N-th refractive index layer on the N-1-th refractive index layer, wherein N is a positive integer greater than or equal to 3.
Further, in the above production method, the refractive index of the even-numbered refractive index layer > the refractive index of the odd-numbered refractive index layer.
Further, in the above preparation method, the first reaction precursor is silane (including monosilane, disilane or other silanes having a substituent), and the second reaction precursor is oxygen or ozone; the third reaction precursor is gas containing titanium, tantalum or zirconium, and the fourth reaction precursor is water vapor or ozone.
Further, in the above manufacturing method, the substrate is a glass, crystal, or sapphire substrate.
Further, in the above production method, the odd-numbered refractive index layers are made of silicon oxide and the even-numbered refractive index layers are made of titanium oxide, tantalum oxide, or zirconium oxide substantially outward from the substrate.
Further, in the above production method, a silicon dioxide layer, a titanium dioxide layer, a silicon dioxide layer, a tantalum pentoxide layer, and a silicon dioxide layer are provided in this order from the substrate substantially outward.
Furthermore, in the preparation method, the temperature is preferably 150-250 ℃.
The technical scheme has the following beneficial effects:
realize the alternate deposition of optical element height, low refractive index rete through ALD (Atomic layer deposition), should the material pass through adsorption and deposition to the substrate base plate with gaseous form in the reaction chamber on, there is not evaporation or sputtering process, has eliminated the source of point defect, consequently can not form the point defect of big granule to the imaging quality of the module of making a video recording is greatly improved, makes ALD obtained the application that has actual nature operation meaning at the course of working of the module of making a video recording.
The other technical scheme of the invention is as follows:
a product of an ALD manufacturing method for eliminating dot defects of a camera module, wherein the camera module comprises a plurality of optical film layers, and the optical film layers are formed through ALD deposition.
Furthermore, the number of dots with the size of more than or equal to 1 μm in the optical film layer is 0.
The technical scheme has the following beneficial effects:
according to the product provided by the invention, the coating of the optical element is realized through atomic layer deposition, the reaction material does not have an evaporation or sputtering process and is deposited on the substrate through adsorption, so that the large-particle point defect is not formed, the imaging quality of the camera module is greatly improved, the product qualification rate is improved, and the optical coating is smoother, higher in firmness and higher in practicability.
Drawings
Fig. 1 is a schematic structural diagram of an optical coating of a camera module according to the present invention.
Fig. 2 is a schematic view of the product of the first embodiment under an eyepiece 10X and an objective 100X of a metallographic microscope.
Fig. 3 is a schematic view of a product of a comparative example under a metallographic microscope eyepiece 10X, an objective lens 100X.
Detailed Description
The invention is further explained with reference to the drawings and the embodiments.
An ALD preparation method for eliminating dot defects of a camera module is characterized by comprising the following steps:
s1: placing a substrate base plate in a reaction cavity, and heating to 100-400 ℃;
s2: introducing a first reaction precursor into the atomic layer reaction cavity, and chemically adsorbing the first reaction precursor on the substrate to form a first film layer;
s3: pumping out excess first reaction precursor and purging with inert gas;
s4: introducing a second reaction precursor into the reaction cavity, and reacting with the first reaction precursor chemically adsorbed on the surface of the substrate base plate to form a first refractive index layer;
s5: pumping excess second reaction precursor and reaction by-products out and purging with an inert gas;
s6: introducing a third reaction precursor into the reaction cavity, and chemically adsorbing the third reaction precursor on the surface of the first refractive index layer to form a second film layer;
s7: pumping out excess third reaction precursor and purging with inert gas;
s8: introducing a fourth reaction precursor into the atomic layer reaction cavity, and reacting with a third reaction precursor chemically adsorbed on the surface of the first refractive index layer to form a second refractive index layer; the refractive index of the second refractive index layer > the refractive index of the first refractive index layer;
s9: excess fourth reaction precursor and reaction by-products are pumped out.
The steps S2-S9 can be repeated periodically to prepare multilayer films with different refractive indexes, namely an Nth refractive index layer is formed on an Nth-1 th refractive index layer, and N is a positive integer greater than or equal to 3. In general, the refractive index of the even-numbered refractive index layers > the refractive index of the odd-numbered refractive index layers. The arrangement of the film layers can increase the light transmittance of the sheet, so that the module has good optical properties, and meanwhile, the micron-sized point defects can be eliminated by using the ALD method, and the imaging quality is improved.
The reaction precursor is determined by the required central wavelength and transmission bandwidth lambda according to the selection of the material, the thickness and the series connection mode of the film layer. In the present invention, the preferred first reactive precursor is silane and the second reactive precursor is oxygen or ozone; the third reaction precursor is a titanium-, tantalum-or zirconium-containing gas (e.g., titanium tetraiodide gas, tantalum pentachloride gas, zirconium tetraiodide gas, or other organic gas containing titanium, tantalum, or zirconium), and the fourth reaction precursor is water vapor or ozone. The temperature and the decomposition temperature of the reaction precursor are related to the deposition rate, and the temperature is required to be below the decomposition temperature of the reaction precursor but have a certain deposition rate.
The substrate is a glass, crystal or sapphire substrate. From the substrate substantially outward, the odd-index layers are silicon oxide and the even-index layers are titanium oxide, tantalum oxide, or zirconium oxide. Preferably, a silicon dioxide layer, a titanium dioxide layer, a silicon dioxide layer, a tantalum pentoxide layer and a silicon dioxide layer can be arranged from the substrate to the outside in sequence.
The temperature of the step S2 and/or S4 is preferably 320-370 ℃; the temperature of the step S6 and/or S8 is preferably 220-270 ℃. The raw material gas can be introduced in a pulse mode, the introduction and the stop of the gas are controlled by controlling the opening and the closing of the electromagnetic valve, and the deposition thickness of the film is influenced by controlling the opening time of the electromagnetic valve.
The product obtained by the method has the number of dots with the size of more than or equal to 1 mu m in the optical film layer of 0.
Example 1
An ALD preparation method for eliminating dot defects of a camera module comprises the following steps:
step S1: firstly, placing a glass substrate into an atomic layer reaction cavity, vacuumizing to 0.6Pa, and heating to 150 ℃;
step S2: using inert gas as carrier, adding SiH4Introducing (silane) serving as a first reaction precursor into the reaction cavity and chemically adsorbing the (silane) on the surface of the substrate to form a first film layer, wherein the gas introduction time is 30-50 ms;
step S3: pumping out excess first reaction precursor (SiH)4) Purging with inert gas (such as helium, argon, etc.) for 20-30 s;
step S4: using inert gas as carrier, adding ozone (O)3) Introducing a second reaction precursor into the atomic layer reaction cavity, wherein the gas introduction time is 20ms, and reacting with the first film layer to form a silicon dioxide low-refractive-index layer L;
step S5: after the reaction is complete, the second reaction precursor, ozone, and the first reaction precursor (SiH) are pumped out4) A by-product of the reaction with the second reaction precursor ozone, purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds;
step S6: taking inert gas as a carrier, taking tantalum pentachloride gas as a third reaction precursor, introducing the third reaction precursor into the reaction cavity, adsorbing the third reaction precursor on the surface of the low-refractive-index layer L, and introducing the gas for 20-30 ms to form a second film layer;
step S7: pumping out the excess third reaction precursor (tantalum pentachloride gas), and purging with inert gas (such as helium, argon, etc.) for 20-30 s;
step S8: taking inert gas as a carrier, introducing water vapor serving as a fourth reaction precursor into the atomic layer reaction cavity, wherein the gas introduction time is 20ms, and reacting with the second film layer to form a tantalum pentoxide refractive index layer H;
step S9: excess fourth reaction precursor (water vapor) and byproducts of the reaction of the third reaction precursor (tantalum pentachloride gas) with the fourth reaction precursor (water vapor) are pumped out and purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds.
The final product is a camera module optical element with a glass substrate coated with a silicon dioxide low refractive index layer L and a tantalum pentoxide high refractive index layer H. The thickness of the low refractive index layer L is 100-200nm, and the refractive index is 1.46-1.50; the thickness of the high-refractive-index layer H is 80-120nm, and the refractive index is 2.05-2.2. The spot condition was monitored by a metallographic microscope, and as shown in FIG. 2, the obtained optical element had no spot defect with a particle size of 1 μm or more. Through batch tests, the product obtained by the preparation method has a defect rate of 0 caused by point defects (the particle size is more than or equal to 5 mu m).
Example 2
An ALD preparation method for eliminating dot defects of a camera module comprises the following steps:
step S1: firstly, placing a glass substrate into a reaction cavity, vacuumizing to 0.6Pa, and heating to 250 ℃;
step S2: adding SiH4(silane) is used as a first reaction precursor and is introduced into the atomic layer reaction cavity and is chemically adsorbed on the surface of the substrate to form a first film layer, and the gas introduction time is preferably 30-50 ms;
step S3: pumping out excess first reaction precursor (SiH)4) Purging with inert gas (such as helium, argon, etc.) for 20-30 s;
step S4: ozone (O)3) Introducing a second reaction precursor into the reaction cavity, wherein the gas is introduced for 20ms and reacts with the first film layer to form a silicon dioxide low-refractive-index layer L;
step S5: after the reaction is complete, the second reaction precursor, ozone, and the first reaction precursor (SiH) are pumped out4) A by-product of the reaction with the second reaction precursor ozone, purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds;
step S6: titanium tetraiodide gas is used as a third reaction precursor and is introduced into the atomic layer reaction cavity, the gas introduction time is preferably 30-50ms, and the gas is adsorbed on the surface of the low-refractive-index layer L to form a second film layer;
step S7: pumping out the excess third reaction precursor (titanium tetraiodide gas), and purging with an inert gas (e.g., helium, argon, etc.) for 20-30 s;
step S8: ozone is used as a fourth reaction precursor and is introduced into the atomic layer reaction cavity, the gas introduction time is 35ms, and the gas reacts with the second film layer to form a titanium dioxide refractive index layer H;
step S9: excess fourth reaction precursor (ozone) and by-products of the reaction of the third reaction precursor (titanium tetraiodide gas) with the fourth reaction precursor (ozone) are pumped out and purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds.
The final product is a camera module optical element with a glass substrate coated with a silicon dioxide low refractive index layer L and a titanium dioxide high refractive index layer H. The thickness of the low refractive index layer L is 100-200nm, and the refractive index is 1.46-1.50; the thickness of the high-refractive-index layer H is 10-50nm, and the refractive index is 2.28-2.35. The spot condition is monitored by a metallographic microscope, and the obtained optical element does not have the spot defect with the grain diameter being more than or equal to 1 mu m.
Example 3
An ALD preparation method for eliminating dot defects of a camera module comprises the following steps:
step S1: firstly, placing a crystal substrate into a reaction chamber, vacuumizing to 0.6Pa, and heating to 400 ℃;
step S2: adding SiH4(silane) serving as a first reaction precursor is introduced into the atomic layer reaction cavity in a pulsed mode and is chemically adsorbed on the surface of the substrate base plate to form a first film layer, and the gas introduction time is preferably 15-20 ms;
step S3: pumping out excess first reaction precursor (SiH)4) Purging with inert gas (such as helium, argon, etc.) for 20-30 s;
step S4: ozone (O)3) Introducing a second reaction precursor into the atomic layer reaction cavity, wherein the gas introduction time is 15-20ms, and the gas reacts with the first film layer to form a silicon dioxide low-refractive-index layer L;
step S5: after the reaction is complete, the second reaction precursor, ozone, and the first reaction precursor (SiH) are pumped out4) A by-product of the reaction with the second reaction precursor ozone, purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds;
step S6: zirconium tetraiodide gas is used as a third reaction precursor and is introduced into the atomic layer reaction cavity, and is adsorbed on the surface of the low-refractive-index layer L, and the gas introduction time is 15-20ms, so that a second film layer is formed;
step S7: pumping out the excess third reaction precursor (zirconium tetraiodide gas), and purging with an inert gas (e.g., helium, argon, etc.) for 20-30 s;
step S8: taking water vapor as a fourth reaction precursor, introducing the water vapor into the atomic layer reaction cavity, and reacting the water vapor with the second film layer, wherein the gas introduction time is 15-20ms, so as to form a titanium dioxide refractive index layer H;
step S9: excess fourth reaction precursor (water vapor) and by-products of the reaction of the third reaction precursor (zirconium tetraiodide gas) with the fourth reaction precursor (water vapor) are pumped out and purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds.
The final product is the camera module optical element with a crystal substrate coated with a silicon dioxide low refractive index layer L and a zirconium dioxide high refractive index layer H. The thickness of the low refractive index layer L is 100-200nm, and the refractive index is 1.46-1.50; the thickness of the high-refractive-index layer H is 35-75nm, and the refractive index is 1.98-2.07. The spot condition is monitored by a metallographic microscope, and the obtained optical element does not have the spot defect with the grain diameter being more than or equal to 1 mu m.
Example 4
An ALD preparation method for eliminating dot defects of a camera module comprises the following steps:
step S1: firstly, placing a sapphire substrate in an atomic layer reaction chamber, vacuumizing to 0.6Pa, and heating to 100 ℃;
step S2: adding SiH4(silane) is used as a first reaction precursor and is introduced into the atomic layer reaction cavity and is chemically adsorbed on the surface of the substrate to form a first film layer, and the gas introduction time is 30-50 ms;
step S3: pumping out excess first reaction precursor (SiH)4) Purging with inert gas (such as helium, argon, etc.) for 20-30 s;
step S4: oxygen (O)2) Introducing the second reaction precursor into the atomic layer reaction chamber for 20-40msAnd reacts with the first film layer to form a silicon dioxide low refractive index layer L;
step S5: after the reaction is complete, the second reaction precursor, ozone, and the first reaction precursor (SiH) are pumped out4) A by-product of the reaction with the second reaction precursor ozone, purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds;
step S6: titanium tetraiodide gas is used as a third reaction precursor and is introduced into the atomic layer reaction cavity, and is adsorbed on the surface of the low-refractive-index layer L, and the gas introduction time is 15-30ms, so that a second film layer is formed;
step S7: pumping out the excess third reaction precursor (titanium tetraiodide gas), and purging with an inert gas (e.g., helium, argon, etc.) for 20-30 s;
step S8: taking water vapor as a fourth reaction precursor, introducing the water vapor into the atomic layer reaction cavity, and reacting the water vapor with the second film layer, wherein the gas introduction time is 15-30ms, so as to form a titanium dioxide refractive index layer H;
step S9: excess fourth reaction precursor (water vapor) and by-products of the reaction of the third reaction precursor (titanium tetraiodide gas) with the fourth reaction precursor (water vapor) are pumped out and purged with an inert gas (e.g., helium, argon, etc.) for 20-30 seconds.
The final product is the camera module optical element with the sapphire substrate covered with the silicon dioxide low refractive index layer L and the titanium dioxide high refractive index layer H. The thickness of the low refractive index layer L is 100-200nm, and the refractive index is 1.47-1.51; the thickness of the high-refractive-index layer H is 10-50nm, and the refractive index is 2.28-2.35. The spot condition is monitored by a metallographic microscope, and the obtained optical element does not have the spot defect with the grain diameter being more than or equal to 1 mu m.
Example 5
An ALD preparation method for eliminating dot defects of a camera module comprises the following steps:
step S1: firstly, placing a sapphire substrate in an atomic layer reaction chamber, vacuumizing to 0.6Pa, and heating to 200 ℃;
step S2: adding SiH4(silane) is used as a first reaction precursor, is introduced into the atomic layer reaction cavity and is chemically adsorbed on the surface of the substrate to formThe gas is introduced into the first film layer for 30-50 ms;
step S3: pumping out excess first reaction precursor (SiH)4) Purging with an inert gas (e.g., helium, argon, etc.) for 15 s;
step S4: oxygen (O)2) Introducing a second reaction precursor into the atomic layer reaction cavity, and reacting with the first film layer to form a silicon dioxide low-refractive-index layer L1;
step S5: after the reaction is complete, the second reaction precursor, ozone, and the first reaction precursor (SiH) are pumped out4) The by-product of the reaction with the second reaction precursor, ozone, is purged with an inert gas (e.g., helium, argon, etc.) for 15 seconds;
step S6: taking tantalum pentachloride gas as a third reaction precursor, introducing the third reaction precursor into the atomic layer reaction cavity, and adsorbing the third reaction precursor on the surface of the low-refractive-index layer L1 to form a second film layer, wherein the gas introduction time is 10-30 ms;
step S7: pumping out excess third reaction precursor (tantalum pentachloride gas) and purging with an inert gas (e.g., helium, argon, etc.) for 15 seconds;
step S8: taking water vapor as a fourth reaction precursor, introducing the water vapor into the atomic layer reaction cavity, and reacting the water vapor with the second film layer to form a titanium dioxide refractive index layer H1;
step S9: pumping out the excess fourth reaction precursor (water vapor) and the by-products of the reaction of the third reaction precursor (tantalum pentachloride gas) with the fourth reaction precursor (water vapor), and purging with an inert gas (e.g., helium, argon, etc.) for 15 s;
step S10: adding SiH4(silane) is used as a fifth reaction precursor and is introduced into the atomic layer reaction cavity and is chemically adsorbed on the surface of the substrate to form a third film layer, and the gas introduction time is 30-50 ms;
step S11: pumping out excess first reaction precursor (SiH)4) Purging with an inert gas (e.g., helium, argon, etc.) for 15 s;
step S12: ozone (O)3) Introducing the precursor serving as a sixth reaction precursor into the atomic layer reaction cavity, and reacting with the first film layer to form a silicon dioxide low-refractive-index layer L2;
step S13: pumping out excess ozone of the second reaction precursor and the fifth reaction precursor (SiH)4) The by-product of the reaction with the sixth reaction precursor, ozone, is purged with an inert gas (e.g., helium, argon, etc.) for 15 seconds;
step S14: taking tantalum pentachloride gas as a seventh reaction precursor, introducing the tantalum pentachloride gas into the atomic layer reaction cavity, and adsorbing the tantalum pentachloride gas on the surface of the low-refractive-index layer L2 to form a fourth film layer, wherein the gas introduction time is 10-30 ms;
step S15: pumping out excess seventh reaction precursor (tantalum pentachloride gas) and purging with an inert gas (e.g., helium, argon, etc.) for 15 seconds;
step S16: taking water vapor as an eighth reaction precursor, introducing the water vapor into the atomic layer reaction cavity, and reacting the water vapor with the fourth film layer to form a tantalum pentoxide refractive index layer H2;
step S17: pumping excess eighth reaction precursor (water vapor) and by-products of the reaction of the seventh reaction precursor (tantalum pentachloride gas) with the eighth reaction precursor (water vapor), purging with an inert gas (e.g., helium, argon, etc.) for 15 seconds;
step S18: adding SiH4(silane) is used as a ninth reaction precursor and is introduced into the atomic layer reaction cavity and adsorbed on the surface of the substrate to form a fifth film layer, and the gas introduction time is 10-50 ms;
step S19: pumping out excess ninth reaction precursor (SiH)4) Purging with an inert gas (e.g., helium, argon, etc.) for 15 s;
step S20: ozone (O)3) Introducing the precursor serving as a tenth reaction precursor into the atomic layer reaction cavity, and reacting with the fifth film layer to form a silicon dioxide low-refractive-index layer L3;
step S21: after the reaction is completed, the excess of the tenth reaction precursor, ozone, and the ninth reaction precursor (SiH) are pumped out4) The by-product of the reaction with the tenth reaction precursor, ozone, is purged with an inert gas (e.g., helium, argon, etc.) for 15 seconds.
The final product is an optical element with 5 optical coating layers covered on the sapphire substrate. The 5 optical coating layers are periodically deposited on the sapphire substrate in a low-refractive-index and high-refractive-index mode, and the last layer is finished in a low-refractive-index mode. The 5 optical coating films are sequentially from the substrate to the outside:
a silicon dioxide low refractive index layer L1 with a layer thickness of 100-200nm and a refractive index of 1.46-1.50;
the titanium dioxide high-refractive-index layer H1 is 10-50nm thick and has a refractive index of 2.28-2.35;
a silicon dioxide low refractive index layer L2 with a layer thickness of 100-200nm and a refractive index of 1.46-1.50;
the tantalum pentoxide high-refractive-index layer H2 is 80-120nm thick and has a refractive index of 2.05-2.2;
the silicon dioxide low refractive index layer L3 has a layer thickness of 5-300nm and a refractive index of 1.46-1.50.
The spot condition is monitored by a metallographic microscope, and the obtained optical element does not have the spot defect with the grain diameter being more than or equal to 1 mu m.
Comparative examples
The target product of this example is the same as the first example, and the vacuum thermal evaporation preparation method comprises the following steps:
step S1: firstly, placing substrate glass in a fixture, placing the fixture on an umbrella stand, and placing the umbrella stand in a coating machine cavity.
Step S2: mixing SiO2(silica) and TiO2The titanium dioxide is respectively put into the crucibles on the left side and the right side in the machine cavity, the bin gate is closed, the vacuum pumping is carried out until the pressure is 0.0001-0.001Pa, the temperature is set within the range of 50-400 ℃, and the machine cavity is always in the range of air pumping.
Step S3: opening SiO2The electron gun at the position of the (silicon dioxide) is operated according to the set film thickness, the operation is finished when the thickness is reached, and the residual molecules are pumped away by gas after the operation is finished; TiO 22The electron gun at the (titanium dioxide) position is automatically turned on for coating.
Step S4: the machine can carry out circulating film coating according to the set number of the film coating layers.
The product of the comparative example was examined for defects by metallographic microscopy, and as a result, defects having a particle size of 5 μm or more were observed as shown in FIG. 3. The same batch test as in example one was carried out, and the product obtained by this production method had a defect rate of 70% due to a point defect (particle diameter. gtoreq.5 μm).
The above embodiments are only for illustrating the invention and are not to be construed as limiting the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention, therefore, all equivalent technical solutions also fall into the scope of the invention, and the scope of the invention is defined by the claims.
Claims (10)
1. An ALD preparation method for eliminating dot defects of a camera module is characterized by comprising the following steps:
s1: placing a substrate base plate in a reaction cavity, and heating to 100-400 ℃;
s2: introducing a first reaction precursor into the atomic layer reaction cavity, and chemically adsorbing the first reaction precursor on the substrate to form a first film layer;
s3: pumping out excess first reaction precursor and purging with inert gas;
s4: introducing a second reaction precursor into the reaction cavity, and reacting with the first reaction precursor chemically adsorbed on the surface of the substrate base plate to form a first refractive index layer;
s5: pumping excess second reaction precursor and reaction by-products out and purging with an inert gas;
s6: introducing a third reaction precursor into the reaction cavity, and chemically adsorbing the third reaction precursor on the surface of the first refractive index layer to form a second film layer;
s7: pumping out excess third reaction precursor and purging with inert gas;
s8: introducing a fourth reaction precursor into the atomic layer reaction cavity, and reacting with a third reaction precursor chemically adsorbed on the surface of the first refractive index layer to form a second refractive index layer; the refractive index of the second refractive index layer > the refractive index of the first refractive index layer;
s9: excess fourth reaction precursor and reaction by-products are pumped out.
2. The ALD preparation method for eliminating dot defects of a camera module according to claim 1, further comprising forming an Nth refractive index layer on the Nth-1 th refractive index layer, wherein N is a positive integer greater than or equal to 3.
3. The ALD preparation method for eliminating dot defects of a camera module according to claim 2, wherein the refractive index of the even-numbered refractive index layer is greater than that of the odd-numbered refractive index layer.
4. The ALD manufacturing method for eliminating dot defects of camera modules according to claim 1, wherein the first reaction precursor is silane, and the second reaction precursor is oxygen or ozone; the third reaction precursor is gas containing titanium, tantalum or zirconium, and the fourth reaction precursor is water vapor or ozone.
5. The ALD preparation method for eliminating dot defects of camera modules according to claim 1, wherein the substrate base plate is a glass, crystal or sapphire base plate.
6. The ALD manufacturing method for eliminating dot defects of a camera module according to claim 3, wherein the odd-numbered refractive index layers are silicon oxide and the even-numbered refractive index layers are titanium oxide, tantalum oxide or zirconium oxide from the substrate substantially outward.
7. The ALD manufacturing method for eliminating dot defects of camera modules according to claim 3, characterized in that a silicon dioxide layer, a titanium dioxide layer, a silicon dioxide layer, a tantalum pentoxide layer and a silicon dioxide layer are arranged from the substrate to the outside in sequence.
8. The ALD preparation method for eliminating dot defects of camera modules according to claim 1, wherein the temperature of the preparation method is preferably 150-250 ℃.
9. The product of the ALD production process for elimination of camera module point sub-defects of claims 1-8, characterized in that the camera module comprises several optical film layers, which are formed by ALD deposition.
10. The product of the ALD manufacturing method for eliminating dot defects of camera modules according to claim 9, wherein the number of dots with the size larger than or equal to 1 μm in the optical film layer is 0.
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| JP2020538658A JP7390296B2 (en) | 2019-11-01 | 2020-05-18 | ALD manufacturing method and its product to eliminate particle defects in imaging module |
| PCT/CN2020/090839 WO2021082402A1 (en) | 2019-11-01 | 2020-05-18 | Ald preparation method for removing photographic module particle defects and product thereof |
| KR1020207020909A KR102456684B1 (en) | 2019-11-01 | 2020-05-18 | ALD manufacturing method and product for reducing dot defects of camera module |
| US16/969,573 US11804501B2 (en) | 2019-11-01 | 2020-05-18 | ALD preparation method for eliminating camera module dot defects and product thereof |
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| WO2021082402A1 (en) * | 2019-11-01 | 2021-05-06 | 杭州美迪凯光电科技股份有限公司 | Ald preparation method for removing photographic module particle defects and product thereof |
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| WO2004075289A1 (en) * | 2003-02-19 | 2004-09-02 | Nippon Electric Glass Co., Ltd. | Cover glass for semiconductor package and method for producing same |
| CN101560653A (en) * | 2009-05-14 | 2009-10-21 | 浙江大学 | Method for preparing gradient-index film |
| CN103773083A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Optical interference color change pigment and its preparation method and application |
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