WO2019085265A1 - 高折射率氢化硅薄膜的制备方法、高折射率氢化硅薄膜、滤光叠层和滤光片 - Google Patents

高折射率氢化硅薄膜的制备方法、高折射率氢化硅薄膜、滤光叠层和滤光片 Download PDF

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WO2019085265A1
WO2019085265A1 PCT/CN2018/071606 CN2018071606W WO2019085265A1 WO 2019085265 A1 WO2019085265 A1 WO 2019085265A1 CN 2018071606 W CN2018071606 W CN 2018071606W WO 2019085265 A1 WO2019085265 A1 WO 2019085265A1
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refractive index
film
nitrogen
oxygen
silicon
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PCT/CN2018/071606
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English (en)
French (fr)
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张睿智
唐健
王迎
余辉
陆张武
徐征驰
张启斌
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浙江水晶光电科技股份有限公司
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Priority to KR1020197011936A priority Critical patent/KR102218167B1/ko
Priority to JP2019523641A priority patent/JP6764532B2/ja
Priority to US16/463,365 priority patent/US11643716B2/en
Publication of WO2019085265A1 publication Critical patent/WO2019085265A1/zh

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Definitions

  • the present invention relates to the field of optical thin film technology, and in particular to a method for preparing a high refractive index hydrogenated silicon film, a high refractive index hydrogenated silicon film, a filter stack, and a filter.
  • Hydrogenated silicon thin films have attracted much attention due to their wide application prospects in microelectronic devices such as infrared imaging sensors, solar cells and thin film transistors.
  • the preparation process of silicon hydride is mainly divided into chemical deposition methods such as plasma enhanced chemical vapor deposition, etc.; physical deposition methods such as radio frequency sputtering.
  • a narrow-band band-pass filter In 3D and other near-infrared imaging systems, a narrow-band band-pass filter is used, which requires that the center wavelength be as small as possible with the angular offset even if the light is incident at a large angle, so as to ensure a wide field of view.
  • the intra-angle signal loss is small and the signal-to-noise ratio is high.
  • the production of such a narrow-band band-pass filter requires the use of an ultra-high-refractive-index coating material and a lower refractive index superimposed on each other.
  • the general film structure is in the tens or even hundreds of layers. The thickness exceeds 8 ⁇ m.
  • each silicon hydride layer is in the range of 800 nm to 1100 nm.
  • the refractive indices in the wavelength range are all greater than 3, and the extinction coefficients in the wavelength range of 800 nm to 1100 nm are all less than 0.0005.
  • This high refractive index silicon hydride layer is implemented on the company's patented coating equipment (sputter deposition system). The sputter deposition system structure is shown in Figure 1.
  • the sputter deposition system activates the passed hydrogen gas through a plasma excitation source (PAS) 460, and overlaps the sputtered silicon material (silicon target) 431 to make the hydrogenated silicon layer at a relatively high deposition rate and relatively low.
  • the hydrogen content is deposited onto the substrate 420.
  • This technique belongs to reactive sputtering, that is, when a target (silicon target) is sputtered in the atmosphere of a reaction gas, the target reacts with a gas to form a compound, hydrogenated silicon.
  • this technique adopts the principle of reactive sputtering, and there may be a case where the target is "poisoned", that is, the target is easily contaminated by hydrogen, causing problems such as unstable production.
  • One of the objects of the present invention is to provide a method for preparing a high refractive index hydrogenated silicon film, which has improved production efficiency and reduced cost, and the obtained oxygen- or nitrogen-containing silicon hydride film has a high refractive index and Lower absorption.
  • Another object of the present invention is to provide a high refractive index hydrogenated silicon film obtained by the method for producing a high refractive index hydrogenated silicon film, which has a high refractive index and low absorption.
  • a third object of the present invention is to provide a filter stack which is obtained by using the oxygen-containing or nitrogen-containing silicon hydride film as a high refractive index material, which has high transmittance and a small central wavelength shift. , the signal loss is small, the signal to noise ratio is high and so on.
  • a fourth object of the present invention is to provide a filter comprising the filter stack, which has the same advantages as the filter stack described above, so that the prepared filter has a higher permeability. Rate and center wavelength offset is small.
  • a method for preparing a high refractive index silicon hydride film comprising the steps of:
  • a silicon film forms an oxygen-containing silicon hydride film in an environment containing active hydrogen and active oxygen, and the amount of active oxygen accounts for 4 to 99% of the total amount of active hydrogen and active oxygen, or
  • the silicon film forms a nitrogen-containing silicon hydride film in an environment containing active hydrogen and reactive nitrogen, and the amount of reactive nitrogen accounts for 5 to 20% of the total amount of active hydrogen and active nitrogen.
  • the amount of active oxygen in the step (b) accounts for 4 to 70% of the total amount of active hydrogen and active oxygen, or the amount of active nitrogen accounts for the total amount of active hydrogen and active nitrogen. 5 to 18%.
  • the amount of active oxygen in step (b) is 5 to 20% of the total amount of active hydrogen and active oxygen, or the amount of active nitrogen is 5 to 10% of the total amount of active hydrogen and active nitrogen.
  • the method for preparing the high refractive index silicon hydride film comprises the following steps:
  • the mixed gas is activated by RF or ICP in the presence of a mixed gas of hydrogen, nitrogen and an inert gas to form a plasma, and the plasma reacts with the silicon film to form a nitrogen-containing silicon hydride film, wherein the nitrogen gas accounts for a mixed gas of hydrogen and nitrogen.
  • the volume percentage is 5 to 20%, preferably 5 to 18%, further preferably 5 to 10%.
  • the Si target sputtering power in the step (a) is 5%-80%, preferably 20%-80%, further preferably 40%-80%, further preferably 40% of the rated power. %-70%, further preferably 50%-70%; and/or, the power of the mixed gas activation by RF or ICP in step (b) is 5%-80%, preferably 5%-50% of the rated power, further It is preferably 15% to 50%, further preferably 20% to 50%.
  • a method for preparing a typical high refractive index silicon hydride film comprises the following steps:
  • the clean substrate is placed on the rotating mechanism of the vacuum sputtering reaction coating machine, the coating surface faces the target, and the rotating mechanism rotates uniformly at the coating chamber; when the vacuum in the coating chamber is higher than 10 -3 Pa, the sputtering is started.
  • the source is argon gas, and is deposited by MF magnetron Si target sputtering on the substrate to form a silicon film;
  • reaction source is RF or ICP plasma excitation source
  • the power of the sputtering source is 5%-80% of the rated power
  • the power of the reaction source is 5%-80% of the rated power
  • the volume of oxygen supplied into the total of hydrogen and oxygen is 4-99%.
  • another method for preparing a high refractive index silicon hydride film comprises the following steps:
  • the clean substrate is placed on the rotating mechanism of the vacuum sputtering reaction coating machine, the coating surface faces the target, and the rotating mechanism rotates uniformly at the coating chamber; when the vacuum in the coating chamber is higher than 10 -3 Pa, the sputtering is started.
  • the source is argon gas, and is deposited by MF magnetron Si target sputtering on the substrate to form a silicon film;
  • reaction source is RF or ICP plasma excitation source
  • the power of the sputtering source is 5%-80% of the rated power
  • the power of the reaction source is 5%-80% of the rated power
  • the volume of nitrogen passing through accounts for 5-20% of the sum of the sum of hydrogen and nitrogen.
  • the rotating mechanism is selected from one of a turntable, a drum and a turret.
  • the coating chamber is provided with a baffle for dividing the coating chamber into the first chamber and the second chamber, the sputtering source is located in the first chamber, and the reaction source is located at the first Two chambers.
  • the coating chamber is provided with a gas mixing chamber, and hydrogen, oxygen and argon gas are respectively introduced into the gas mixing chamber, and uniformly mixed and then introduced into the coating chamber for activation; or
  • Hydrogen, nitrogen and argon are respectively introduced into the gas mixing chamber, mixed uniformly and then introduced into the coating chamber for activation.
  • the method further comprises heating the substrate to a substrate temperature of 100-300 ° C, and then introducing an argon gas to the coating chamber and the substrate. Bombardment cleaning; after cleaning, argon gas is turned off, and the vacuum in the coating chamber is again pumped to above 10 -3 Pa;
  • the bombardment cleaning time is 1 to 5 minutes, and the bombardment power is 5% to 80% of the rated power.
  • the oxygen-containing silicon hydride film or the nitrogen-containing silicon hydride film is further annealed in an annealing furnace at 100-300 ° C for 60-180 min.
  • annealing the oxygen-containing silicon hydride film or the nitrogen-containing silicon hydride film in the annealing furnace comprises:
  • the temperature was then lowered to room temperature at a rate of 10-30 ° C/min.
  • a high refractive index hydrogenated silicon film obtained by the above method for preparing a high refractive index hydrogenated silicon film having a refractive index of 1.46 to 3.7 in a wavelength range of 800 to 1100 nm is provided.
  • the high refractive index hydrogenated silicon film has an extinction coefficient of less than 0.0001 in a wavelength range of 800 to 1100 nm.
  • a filter stack comprising a plurality of the above-mentioned high refractive index hydrogenated silicon film and a plurality of low refractive index films, wherein a plurality of high refractive index hydrogenated silicon films and a plurality of low refractive index films are alternately stacked, wherein
  • the low refractive index film is a film having a refractive index in a wavelength range of 800 to 1100 nm that is smaller than a refractive index of the high refractive index hydrogenated silicon film in a wavelength range of 800 to 1100 nm.
  • the low refractive index film is a silicon dioxide film
  • the low refractive index film is a low refractive index hydrogenated silicon film, and the low refractive index film has a refractive index in a wavelength range of 800 to 1100 nm smaller than that of the high refractive index silicon hydride film in a wavelength range of 800 to 1100 nm. Rate of film;
  • the number of layers of the filter stack is 10 to 100 layers;
  • the filter laminate has a thickness of from 1 to 10 ⁇ m.
  • a filter comprising the above filter stack.
  • the present invention has the following beneficial effects:
  • the preparation method of the high refractive index hydrogenated silicon film of the present invention firstly uses magnetron sputtering, magnetron sputtering, sputtering, depositing Si on a substrate, forming a silicon thin film, and then passing a hydrogenation reaction in an environment containing active hydrogen.
  • the formation of the silicon hydride film, the sputtering process and the reaction process are separated, relatively independent, the target of the sputtering process is not easily contaminated by the reaction gas, and the target poisoning problem is effectively avoided.
  • the method for preparing a high refractive index hydrogenated silicon film of the present invention has a refractive index of 1.46 to 3.7 in a wavelength range of 800 to 1100 nm, an extinction coefficient of less than 0.0001 in a wavelength range of 800 to 1100 nm, and a film refraction. High rate and low absorption.
  • the filter stack of the present invention uses the oxygen-containing or nitrogen-containing silicon hydride film as a high refractive index material, and a lower refractive index lower than the above refractive index such as silicon oxide, high oxygenated silicon hydride or the like.
  • the materials are alternately stacked to form a high-transmittance filter stack, and the filter stack is plated on the glass or resin substrate to form optical interference film bandpass, long-wavelength, short-wavepass and other filters to make the light at a large angle.
  • the center wavelength shift of the filter is small at the time of incidence, which makes the sensor have less signal loss and high signal-to-noise ratio in a large angle of view. It can be applied to night vision, 3D imaging, 3D modeling, and face. Identification, iris recognition, gesture recognition, etc. All filters, sensor systems that require low offset effects.
  • the filter of the present invention comprises the above-described filter stack, and thus has the same advantages as the above-described filter stack, so that the produced filter has a high transmittance and a central wavelength shift amount. small.
  • FIG. 1 is a schematic structural view of a prior art sputter deposition system
  • FIG. 2 is a schematic structural view of a vacuum sputtering reaction coating system according to an embodiment of the present invention
  • Figure 3 is the effect of the ratio of oxygen to hydrogen-oxygen mixed gas at 940 nm on the refractive index and extinction coefficient of the silicon oxyhydroxide film
  • (a) is the ratio of oxygen to oxygen-oxygen mixed gas at 940 nm to the refractive index of the silicon oxyhydroxide film.
  • Effect, (b) is the effect of the ratio of oxygen to hydrogen-oxygen mixed gas at 940 nm on the extinction coefficient of the silicon oxyhydroxide film);
  • Figure 4 is the effect of the ratio of oxygen to hydrogen-oxygen mixed gas at 850 nm on the refractive index and extinction coefficient of the silicon oxyhydroxide film
  • (a) is the ratio of oxygen to oxygen-oxygen mixed gas at 940 nm to the refractive index of the silicon oxyhydroxide film.
  • Effect, (b) is the effect of the ratio of oxygen to hydrogen-oxygen mixed gas at 940 nm on the extinction coefficient of the silicon oxyhydroxide film);
  • Figure 5 is the effect of the ratio of nitrogen to hydrogen-nitrogen mixed gas at 940 nm on the refractive index and extinction coefficient of nitrogen-containing silicon hydride film
  • (a) is the ratio of nitrogen to hydrogen-nitrogen mixed gas at 940 nm to the refractive index of nitrogen-containing silicon hydride film.
  • Effect, (b) is the effect of the ratio of nitrogen to hydrogen-nitrogen mixed gas at 940 nm on the extinction coefficient of nitrogen-containing silicon hydride film);
  • Example 6 is a measured spectral curve of a 940 nm center wavelength band pass filter 0-30° incident using the filter stack of Example 28.
  • Example 7 is a measured spectral curve of a 850 nm central wavelength bandpass filter implanted at 0-30[deg.] using the filter stack of Example 28.
  • Example 8 is a measured spectral curve of a 940 nm center wavelength band pass filter 0-30° incident using the filter stack of Example 29.
  • Figure 9 is a measured spectrum of the 0-40° incidence of a 940 nm center wavelength bandpass filter plated using a TiO 2 filter stack.
  • a method of preparing a high refractive index silicon hydride film comprising the steps of:
  • a silicon film forms an oxygen-containing silicon hydride film in an environment containing active hydrogen and active oxygen, and the amount of active oxygen accounts for 4 to 99% of the total amount of active hydrogen and active oxygen, or
  • the silicon film forms a nitrogen-containing silicon hydride film in an environment containing active hydrogen and reactive nitrogen, and the amount of reactive nitrogen accounts for 5 to 20% of the total amount of active hydrogen and active nitrogen.
  • the Si target is a semiconductor high-purity silicon material in a single crystal or polycrystalline form.
  • Typical but non-limiting substrates are, for example, single crystal Si sheets, glass sheets or resin sheets.
  • magnetron sputtering is used to deposit a magnetron Si target, and Si is deposited on the substrate to form a silicon thin film.
  • Magnetron sputtering is a kind of physical vapor deposition (PVD). It has the advantages of simple equipment, easy control, large coating area and strong adhesion. Magnetron sputtering can be carried out in a vacuum plating sputter coater.
  • the Si target is mounted on a medium frequency (MF) or radio frequency (RF) cathode, and an inert gas is introduced into the vacuum chamber (typical but not limited).
  • MF medium frequency
  • RF radio frequency
  • argon gas argon gas
  • argon gas is ionized to form a plasma
  • a high-purity silicon target is bombarded by electric and magnetic fields, and the silicon material is sputtered onto the substrate to form a silicon thin film.
  • active hydrogen can be obtained by activating hydrogen, and both atomic and molecular forms of active hydrogen are considered to exist in the plasma, and the active hydrogen is more chemically active, so that Si-H bonds can be formed with Si.
  • the same reactive oxygen species can be obtained by activating oxygen, which can form Si-O bonds, which can be obtained by activating nitrogen gas to form Si-N bonds.
  • hydrogen and oxygen may be excited by a radio frequency (RF) or ICP (Inductive Coupled Plasma Emission Spectrometer) excitation source, or hydrogen and nitrogen may be excited to obtain active hydrogen and active oxygen, or active hydrogen. And reactive nitrogen, thereby reacting with silicon to obtain oxygenated silicon hydride or nitrogenated silicon hydride.
  • RF radio frequency
  • ICP Inductive Coupled Plasma Emission Spectrometer
  • the oxygen content or nitrogen content in the silicon hydride has an important influence on the refractive index and absorption of the film.
  • the amount of active oxygen is controlled to be 4 to 99% of the total amount of active hydrogen and active oxygen, for example, 4%. Range values between one or both of 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, and 99%.
  • the amount of active nitrogen is controlled to be 5 to 20% of the total amount of active hydrogen and active nitrogen, for example, 5%. Range values between one or any of 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, and 20%.
  • a refractive index of 1.46-3.7 at 800-1100 nm, a high refractive index of less than 0.0001, and a low extinction coefficient can be obtained. Absorbed silicon hydride film.
  • a refractive index of 3.0-3.3 at 800-1100 nm and a high refractive index of less than 0.0001 at an extinction coefficient can be obtained. Absorbed silicon hydride film.
  • the active oxygen/nitrogen content is too low, which is not well controlled.
  • the active nitrogen content is too high, although the refractive index is relatively high, the extinction coefficient is large, and the desired film layer cannot be obtained.
  • a silicon hydride thin film is obtained by a hydrogenation reaction, and a certain amount of oxidation reaction or nitridation reaction occurs simultaneously with the hydrogenation reaction to form a high refractive index, low absorption silicon oxyhydroxide film or a silicon nitride containing silicon hydride film.
  • the process can be carried out in the same vacuum plating sputter coater as the above step (a), but it should be noted that the two processes are performed separately.
  • the method for obtaining silicon hydride in the prior art is by a reactive sputtering method in which sputtering and reaction are simultaneously performed, and the target material is sputtered in a reaction gas atmosphere, and the target material is easily contaminated with hydrogen, causing problems such as unstable production.
  • a baffle is used to divide the coating chamber into a first chamber and a second chamber, the sputtering source is located in the first chamber, and the reaction source is located in the second chamber.
  • the segmentation in this embodiment is not completely independent and sealed.
  • the substrate on the rotating mechanism drives the substrate into the first chamber for sputtering by the rotation of the rotating mechanism. After the sputtering is completed, the second chamber is reacted with the mixed gas.
  • the sputtering source and the reaction source are physically distinguished by the baffle, and when the sputtering source and the reaction source are disposed, the positional distance between the sputtering source and the reaction source is expanded as much as possible to achieve relative independence.
  • the target of the sputtering process is not easily contaminated by the reaction gas, and the poisoning problem of the target is effectively avoided.
  • the preparation method of the present invention firstly uses a magnetron sputtering method, a magnetron-controlled Si target sputtering, deposits Si on a substrate, forms a silicon thin film, and then forms a silicon hydride film by hydrogenation reaction in an environment containing active hydrogen, a sputtering process and The reaction process is separate and relatively independent.
  • the target of the sputtering process is not easily contaminated by the reaction gas, and the target poisoning problem is effectively avoided.
  • a specific proportion of active oxygen or reactive nitrogen is added to the active hydrogen-containing environment, and an oxidation reaction or a nitridation reaction occurs simultaneously with the hydrogenation reaction to form an oxygen-containing silicon hydride film or a nitrogen-containing silicon hydride film, the oxygen-containing silicon hydride.
  • the film or nitrogen-containing silicon hydride film has a higher refractive index and lower absorption.
  • the method can be realized in a conventional simple vacuum sputtering coating apparatus or system, which improves production efficiency and reduces production cost.
  • the amount of active oxygen in step (b) is 4 to 70% of the total amount of active hydrogen and active oxygen, or the amount of active nitrogen is 5 to 18% of the total amount of active hydrogen and active nitrogen.
  • the amount of active oxygen in the step (b) is 5 to 20% of the total amount of the active hydrogen and the active oxygen, or the amount of the active nitrogen is 5 to 10% of the total amount of the active hydrogen and the active nitrogen.
  • the silicon hydride film having a lower oxygen content/nitrogen content has Higher refractive index and lower absorption.
  • the method for preparing a high refractive index silicon hydride film comprises the following steps:
  • the mixed gas is activated by RF or ICP in the presence of a mixed gas of hydrogen, nitrogen and an inert gas to form a plasma, and the plasma reacts with the silicon film to form a nitrogen-containing silicon hydride film, wherein the nitrogen gas accounts for a mixed gas of hydrogen and nitrogen.
  • the volume percentage is 5 to 20%, preferably 5 to 18%, further preferably 5 to 10%.
  • a typical, but non-limiting, inert gas is argon.
  • This step can be carried out in a vacuum sputtering reaction coater by sputtering a single crystal or polycrystalline form of a semiconductor silicon material using a plasma such as argon to cause the silicon material to be sputtered onto the glass substrate in a nanometer size.
  • a reaction source having an ICP or RF function is used, and a plasma is mixed with a mixture of hydrogen, oxygen, and argon or a mixed gas of hydrogen, nitrogen, and argon to form a plasma, and the silicon material is subjected to hydrogen oxidation or hydrogen nitridation treatment, and finally A certain amount of oxygenated or nitrogen-containing silicon hydride film is formed.
  • the coating chamber is provided with a gas mixing chamber, and hydrogen, oxygen and argon are respectively introduced into the gas mixing chamber, and uniformly mixed and then introduced into the coating chamber for activation; or, hydrogen, nitrogen and argon are respectively introduced into the gas mixing chamber, After mixing, it is passed into the coating chamber for activation.
  • the invention can disperse and mix hydrogen, oxygen and argon uniformly by setting a gas mixing chamber, so that when the mixed gas is activated by RF or ICP, the effect is better, and the hydrogen, oxygen and argon are directly introduced without being mixed. The resulting activation effect is not uniform.
  • the volume percentage of oxygen to the mixed gas of hydrogen and oxygen is 4 to 99%, for example, 4%, 5%, 10%, 20%, 30%, 40%, 50%.
  • the range value between any one of 60%, 70%, 80%, 90%, 95%, and 99%, or any two, is, for example, preferably 4 to 70%, and further preferably, for example, 5 to 20%.
  • nitrogen accounts for 5 to 20% by volume of the mixed gas of hydrogen and nitrogen, for example, 5%, 6%, 8%, 10%, 12%, 14%, 15%.
  • the range value between any one of 16%, 18%, and 20%, or both, is, for example, preferably 5 to 18%, and further preferably, for example, 5 to 10%.
  • the oxygen or nitrogen gas introduced is too low, which is not well controlled.
  • the volume of nitrogen is too high, although the refractive index is relatively high, the extinction coefficient is large, and the desired film layer cannot be obtained.
  • the sputtering power of the Si target in the step (a) is 5% to 80%, preferably 20% to 80%, further preferably 40% to 80%, further preferably 40% to 70% of the rated power. % is further preferably 50% to 70%.
  • the rated power of the Si target sputtering is, for example, 15 KW.
  • the Si target sputtering power in the step (a) is typically, but not limited to, 0.75 KW, 1.5 KW, 3 KW, 6 KW, 7 KW, 8 KW, 9 KW, 10 KW, 11 KW, and 11 KW. Range values between any and any of 12 KW.
  • the power of the mixed gas activated by RF or ICP in step (b) is 5%-80%, preferably 5%-50%, further preferably 15%-50% of the rated power, further It is preferably 20% to 50%.
  • the power of the mixed gas activation by RF or ICP typically refers to the power of the reaction source having an ICP or RF function, and the rated power of the reaction source power is, for example, 10 KW, at which time the reaction source power is typically, but not limited to, 0.5 KW, 1 KW, for example. Range values between any of 2KW, 3KW, 4KW, 5KW, 6KW, 7KW, and 8KW, or any two.
  • the refractive index and absorption of the film are also affected. Therefore, in order to obtain a film with high refractive index and small absorption, it is necessary to adjust the parameters such as sputtering power and reaction power.
  • the specific values of the parameters of different machines may be slightly different, and can be adjusted according to the actual situation.
  • a method for preparing a typical high refractive index oxygen-containing silicon hydride film comprises the following steps:
  • the clean substrate is placed on the rotating mechanism of the vacuum sputtering reaction coating machine, the coating surface faces the target, and the rotating mechanism rotates uniformly at the coating chamber; when the vacuum in the coating chamber is higher than 10 -3 Pa, the sputtering is started.
  • the source is argon gas, and is deposited by MF magnetron Si target sputtering on the substrate to form a silicon film;
  • reaction source is RF or ICP plasma excitation source
  • the power of the sputtering source is 5%-80% of the rated power
  • the power of the reaction source is 5%-80% of the rated power
  • the volume of oxygen supplied into the total of hydrogen and oxygen is 4-99%.
  • the rated power of the sputtering source is, for example, 15 kW, and the power of the sputtering source is typically, but not limited to, for example, any of 0.75 KW, 1.5 KW, 3 KW, 6 KW, 7 KW, 8 KW, 9 KW, 10 KW, 11 KW, and 12 KW.
  • the range value between any two, the rated power of the reaction source is, for example, 10 KW, and the power of the reaction source at this time is typically, but not limited to, 0.5 KW, 1 KW, 2 KW, 3 KW, 4 KW, 5 KW, 6 KW, 7 KW, for example,
  • the range value between any one of 8KW and any two, the volume percentage of oxygen supplied to the sum of hydrogen and oxygen is, for example, 4%, 5%, 10%, 20%, 30%, 40%. Range values between any of 50%, 60%, 70%, 80%, 90%, 95%, and 99%, or any combination.
  • the volume of oxygen supplied to the mixed gas of hydrogen and oxygen can be achieved by adjusting the flow rate (sccm) of each gas.
  • a method for preparing a typical high refractive index oxygen-containing silicon hydride film comprises the following steps:
  • reaction source is RF or ICP plasma excitation source
  • the oxygenated silicon hydride film is annealed by a specific annealing process and parameters, and specific parameters such as temperature increase rate, temperature drop rate, annealing time, etc. are defined, which is beneficial to improve the structure and optical properties and exhibit better heat stability.
  • a method for preparing a typical high refractive index nitrogen-containing silicon hydride film comprises the following steps:
  • the clean substrate is placed on the rotating mechanism of the vacuum sputtering reaction coating machine, the coating surface faces the target, and the rotating mechanism rotates uniformly at the coating chamber; when the vacuum in the coating chamber is higher than 10 -3 Pa, the sputtering is started.
  • the source is argon gas, and is deposited by MF magnetron Si target sputtering on the substrate to form a silicon film;
  • reaction source is RF or ICP plasma excitation source
  • the power of the sputtering source is 5%-80% of the rated power
  • the power of the reaction source is 5%-80% of the rated power
  • the volume of nitrogen passing through accounts for 5-20% of the sum of the sum of hydrogen and nitrogen.
  • the rated power of the sputtering source is, for example, 15 kW, and the power of the sputtering source is typically, but not limited to, for example, any of 0.75 KW, 1.5 KW, 3 KW, 6 KW, 7 KW, 8 KW, 9 KW, 10 KW, 11 KW, and 12 KW.
  • the range value between any two, the rated power of the reaction source is, for example, 10 KW, and the power of the reaction source at this time is typically, but not limited to, 1.5 KW, 2 KW, 3 KW, 4 KW, 5 KW, 6 KW, 7 KW, and 8 KW, for example.
  • the volume of nitrogen introduced into the mixed gas of hydrogen and nitrogen can be achieved by adjusting the flow rate (sccm) of each gas.
  • a method for preparing a typical high refractive index nitrogen-containing silicon hydride film comprises the following steps:
  • reaction source is RF or ICP plasma excitation source
  • the nitrogen-containing silicon hydride film is annealed by a specific annealing process and parameters, and specific parameters such as temperature increase rate, temperature drop rate, annealing time, etc. are defined, which is beneficial to improve the structure and optical properties and exhibit better heat stability.
  • Sex The preparation method of the typical oxygen-containing silicon hydride film or the nitrogen-containing silicon hydride film can be carried out in a vacuum sputtering reaction coating system.
  • FIG. 2 is a schematic structural view of a vacuum sputtering reaction coating system according to an embodiment of the present invention.
  • the clean substrate 100 is placed on the rotating mechanism 200 with the coating surface facing the target;
  • the rotating mechanism 200 rotates at a uniform speed in the coating chamber 500;
  • the substrate is heated to a temperature of 100-300 ° C, and then the coating chamber and the substrate are bombarded with argon gas; after the cleaning is completed, the argon gas is turned off, and again The vacuum in the coating chamber is pumped to above 10 -3 Pa; the sputtering source 300 located in the first chamber is opened and argon gas is passed through, and the argon gas is ionized to form a plasma, and the high-purity silicon target is bombarded under the action of electric and magnetic fields. Silicon material is sputtered onto the substrate 100;
  • the substrate 100 is carried to a reaction source (RF/ICP) region located in the second chamber, and the sputtering source 300 and the reaction source 400 are spaced apart by the spacer 600;
  • RF/ICP reaction source
  • the reaction source 400 is filled with hydrogen, oxygen and argon.
  • the hydrogen, oxygen and argon are uniformly mixed in the gas mixing chamber 700 and then discharged to form a plasma, which is moved to the substrate 100 at a high speed by the electric field.
  • the silicon film on the substrate 100 is reacted to synthesize an oxygen-containing silicon hydride film.
  • the oxygenated silicon hydride film is heated in an annealing furnace at a heating rate of 1-15 ° C / min to 100-300 ° C for 30-60 min; then kept at a constant temperature of 100-300 ° C for 30 -120 min; then cooled to room temperature at a rate of 10-30 ° C / min, and taken out.
  • the power parameter range of the sputtering source is 5%-80% of the rated power
  • the power parameter range of the reaction source is 5%-80% of the rated power
  • the volume of oxygen supplied into the sum of hydrogen and oxygen is 4 ⁇ 99%.
  • the time of bombardment cleaning is 1 to 5 minutes, and the bombardment power is 5%-80% of the rated power.
  • the rotating mechanism 200 may be selected from one of a turntable, a drum, and a turret.
  • the clean substrate 100 is placed on the rotating mechanism 200 with the coating surface facing the target;
  • the rotating mechanism 200 rotates at a uniform speed in the coating chamber 500;
  • the substrate is heated to a temperature of 100-300 ° C, and then the coating chamber and the substrate are bombarded with argon gas; after the cleaning is completed, the argon gas is turned off, and again The vacuum in the coating chamber is pumped to above 10 -3 Pa; the sputtering source 300 located in the first chamber is opened and argon gas is passed through, and the argon gas is ionized to form a plasma, and the high-purity silicon target is bombarded under the action of electric and magnetic fields. Silicon material is sputtered onto the substrate 100;
  • the substrate 100 is carried to a reaction source (RF/ICP) region located in the second chamber, and the sputtering source 300 and the reaction source 400 are spaced apart by the spacer 600;
  • RF/ICP reaction source
  • the reaction source 400 is connected with hydrogen, nitrogen and argon, and hydrogen, nitrogen and argon are uniformly mixed in the gas mixing chamber and then discharged to form a plasma, which is moved to the substrate 100 at a high speed under the action of the electric field, and finally with the substrate.
  • the silicon film on 100 reacts to synthesize a nitrogen-containing silicon hydride film.
  • the nitrogen-containing silicon hydride film is heated in an annealing furnace at a heating rate of 1-15 ° C / min to 100-300 ° C for 30-60 min; then kept at a constant temperature of 100-300 ° C for 30 -120 min; then cooled to room temperature at a rate of 10-30 ° C / min, and taken out.
  • the power parameter range of the sputtering source is 5%-80% of the rated power
  • the power parameter range of the reaction source is 5%-80% of the rated power
  • the volume of nitrogen introduced into the sum of the hydrogen and nitrogen is 5 ⁇ 20%.
  • the time of bombardment cleaning is 1 to 5 minutes, and the bombardment power is 5%-80% of the rated power.
  • the rotating mechanism 200 may be selected from one of a turntable, a drum, and a turret.
  • the glass substrate is arranged on the rotating mechanism dome cover, and the rotation speed is adjustable counterclockwise with the rotating mechanism dome cover, and the coated substrate is first passed through a sputtering source, and a thin layer of silicon is deposited, and then rotated to the reaction.
  • the source is an optical film which is synthesized by a plasma consisting of argon-hydrogen argon or hydrogen-nitrogen argon ions and electrons.
  • the minimum refractive index of 800 to 1100 nm can be gradually changed from 1.46 to 3.7, and extinction is performed.
  • the gas charged by the reaction source is a mixed gas of hydrogen, oxygen and argon with a high proportion of oxygen, or a mixed gas of pure oxygen, hydrogen and argon
  • the refractive index of 800 to 1100 nm can be gradually changed from 1.46 to 1.7, and extinction is completed.
  • the proportion of oxygen or nitrogen in the mixed gas of the reaction source is an important parameter, and if a film having a high refractive index and a small absorption is to be obtained, it is necessary to adjust the parameters such as sputtering power and reaction power.
  • the specific values of the parameters of different machines will be different.
  • a high refractive index hydrogenated silicon film obtained by the above-described method for producing a high refractive index hydrogenated silicon film.
  • the high refractive index hydrogenated silicon film has a refractive index of 1.46 to 3.7 in a wavelength range of 800 to 1100 nm, and the high refractive index hydrogenated silicon film has an extinction coefficient of less than 0.0001 in a wavelength range of 800 to 1100 nm.
  • a filter stack comprising a plurality of the above-mentioned high refractive index silicon hydride film and a plurality of low refractive index films, a plurality of high refractive index silicon hydride films and a plurality of low refractive indices The films are stacked alternately.
  • the low refractive index film refers to a film having a refractive index in the wavelength range of 800 to 1100 nm which is smaller than the refractive index of the high refractive index hydrogenated silicon film of the present invention in the wavelength range of 800 to 1100 nm.
  • the low refractive index film is a silicon dioxide film.
  • the silicon dioxide film generally has a refractive index of between 1.46 and 1.50, and belongs to a lower refractive index film, which is alternately stacked with the hydrogenated silicon film of the present invention above the refractive index to form a filter stack.
  • the low refractive index film is a low refractive index hydrogenated silicon film.
  • the low refractive index silicon hydride film referred to herein is a relative refractive index which means that the refractive index of the hydrogenated silicon film in the laminated film structure is smaller than that of the high refractive index silicon hydride film of the present invention.
  • the hydrogenated silicon film obtained by the method of the present invention has a refractive index of 3
  • the low refractive index hydrogenated silicon film refers to all of the silicon hydride films having a refractive index lower than 3, and may be a silicon hydride film obtained by a conventional method, or may be A silicon hydride film having a high oxygen content is obtained by the method of the present invention.
  • the number of layers of the filter stack is 10 to 100 layers;
  • the filter laminate has a thickness of from 1 to 10 ⁇ m.
  • the filter stack includes a plurality of silicon hydride films and a plurality of low refractive index layers serving as a high refractive index layer, and a plurality of silicon hydride films are alternately stacked with a plurality of low refractive index layers.
  • the filter stack may be composed of a plurality of silicon hydride layers and a plurality of low refractive index layers stacked in a sequence of (high/low) n, (high/low) n high or low (high/low) n.
  • the filter stack comprises a total of 10 to 100 layers, i.e. 5 ⁇ n ⁇ 50.
  • each of the hydrogenated silicon layer and the low refractive index layer has a thickness of from 3 to 300 nm, and the filter stack has a thickness of from 1 to 10 ⁇ m.
  • the number of layers and thickness are chosen according to the specific optical design.
  • a filter comprising the above filter stack.
  • Typical, but non-limiting, filters are, for example, band pass, long pass or short pass filters.
  • the filter stack of the present invention uses the oxygen-containing or nitrogen-containing silicon hydride film as a high refractive index material, and is alternately stacked with a lower refractive index material such as silicon oxide, high oxygenated silicon hydride, or lower than the above refractive index.
  • a high-transmission filter stack is formed, and the filter stack is plated on the glass or resin substrate to form optical interference film bandpass, long-wavelength, short-wavepass and other filters, so that the light is filtered at a large angle.
  • the center wavelength shift of the light sheet is small, which makes the sensor have less signal loss and high signal-to-noise ratio in a large angle of view. It can be applied to night vision, 3D imaging, 3D modeling, face recognition, iris. Identification, gesture recognition, etc. All filters, sensor systems that require low offset effects.
  • the preparation method of the high refractive index oxygen/nitrogen-containing silicon hydride film of the embodiment is carried out by using a NSP1650 sputter coating system (shown in FIG. 2) of Guangchi Technology Co., Ltd., and the substrate is a glass substrate.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film comprises the following steps:
  • the power of the reaction source is 2 KW, and the reaction source area is supplied with hydrogen, oxygen and argon gas to adjust the gas flow rate so that the volume of oxygen supplied to the sum of hydrogen and oxygen is 6%, and the gas is excited.
  • the plasma is formed, and the substrate is moved at a high speed by the electric field, and finally reacts with the silicon film on the substrate to form an oxygen-containing silicon hydride film.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film wherein the oxygen in the step (e) accounts for 14% by volume of the sum of hydrogen and oxygen, and the remaining steps and parameters are the same as in the first embodiment.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film wherein the oxygen in the step (e) accounts for 23% by volume of the sum of hydrogen and oxygen, and the remaining steps and parameters are the same as in the first embodiment.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film wherein the oxygen in the step (e) accounts for 58% by volume of the sum of hydrogen and oxygen, and the remaining steps and parameters are the same as in the first embodiment.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film wherein the oxygen in the step (e) accounts for 62% by volume of the sum of hydrogen and oxygen, and the remaining steps and parameters are the same as in the first embodiment.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film wherein the oxygen in the step (e) accounts for 67% by volume of the sum of hydrogen and oxygen, and the remaining steps and parameters are the same as in the first embodiment.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film wherein the oxygen in the step (e) accounts for 71% by volume of the sum of hydrogen and oxygen, and the remaining steps and parameters are the same as in the first embodiment.
  • step (c) A method for preparing a high refractive index oxygen-containing silicon hydride film, wherein the sputtering source power in step (c) is 6 KW, and the remaining steps and parameters are the same as in the first embodiment.
  • step (c) A method for preparing a high refractive index oxygen-containing silicon hydride film, wherein the sputtering source power in step (c) is 12 KW, and the remaining steps and parameters are the same as in the first embodiment.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film wherein the sputtering source power is 1 KW in the step (c), and the remaining steps and parameters are the same as in the first embodiment.
  • step (c) A method for preparing a high refractive index oxygen-containing silicon hydride film, wherein the sputtering source power in step (c) is 20 KW, and the remaining steps and parameters are the same as in the first embodiment.
  • step (e) A method for preparing a high refractive index oxygen-containing silicon hydride film, wherein the reaction source power in step (e) is 0.5 KW, and the remaining steps and parameters are the same as in the first embodiment.
  • step (e) A method for preparing a high refractive index oxygen-containing silicon hydride film, wherein the reaction source power in step (e) is 5 KW, and the remaining steps and parameters are the same as in the first embodiment.
  • step (e) A method for preparing a high refractive index oxygen-containing silicon hydride film, wherein the reaction source power in step (e) is 10 KW, and the remaining steps and parameters are the same as in the first embodiment.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film comprises the following steps:
  • the power of the reaction source is 2 KW, and the reaction source area is connected with hydrogen, oxygen and argon gas to adjust the gas flow rate so that the volume of oxygen supplied to the sum of hydrogen and oxygen is 6%, hydrogen and oxygen.
  • the gas After being uniformly mixed with the argon gas in the gas mixing chamber, the gas is excited to form a plasma, and moves to the substrate at a high speed under the action of the electric field, and finally reacts with the silicon film on the substrate to form an oxygenated silicon hydride film.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film comprises the following steps:
  • the power of the reaction source is 2 KW, and the reaction source area is connected with hydrogen, oxygen and argon gas to adjust the gas flow rate so that the volume of oxygen supplied to the sum of hydrogen and oxygen is 6%, hydrogen and oxygen.
  • the gas After being uniformly mixed with the argon gas in the gas mixing chamber, the gas is excited to form a plasma, and moves to the substrate at a high speed under the action of the electric field, and finally reacts with the silicon film on the substrate to form an oxygen-containing silicon hydride film.
  • a method for preparing a high refractive index oxygen-containing silicon hydride film comprises the following steps:
  • the power of the reaction source is 2 KW, and the reaction source area is connected with hydrogen, oxygen and argon gas to adjust the gas flow rate so that the volume of oxygen supplied to the sum of hydrogen and oxygen is 6%, hydrogen and oxygen.
  • the gas After being uniformly mixed with the argon gas in the gas mixing chamber, the gas is excited to form a plasma, and moves to the substrate at a high speed under the action of the electric field, and finally reacts with the silicon film on the substrate to form an oxygenated silicon hydride film.
  • a method for preparing a silicon dioxide film wherein oxygen and argon are introduced into step (e), and hydrogen gas is not supplied, and the remaining steps and parameters are the same as in the first embodiment to obtain a silicon dioxide film.
  • the oxygen-containing silicon hydride film obtained by the methods of Examples 1-21 and Comparative Example 1 was measured for refractive index and extinction coefficient at 940 nm, and the measurement method was measured by a conventional method in the art.
  • the oxygen-containing silicon hydride film obtained by the method of the present invention (oxygen in the proportion of hydrogen-oxygen mixed gas of 4 to 99%) has a refractive index at 940 nm of 1.46 to 3.7.
  • Figure 3 shows the effect of the ratio of oxygen to hydrogen-oxygen mixed gas at 940 nm on the refractive index and extinction coefficient of the silicon oxyhydroxide film.
  • the ratio of oxygen to hydrogen-oxygen mixed gas has an influence on the refractive index and extinction coefficient of the silicon oxyhydroxide film.
  • the refractive index and extinction coefficient of the silicon hydride film gradually decrease.
  • the oxygen ratio is up to 100%, that is, in the case of Comparative Example 1, when no hydrogen is present, the resulting film is a silicon dioxide film, and the silicon dioxide film has a lower refractive index.
  • the sputtering source power is smaller than that in the first embodiment, and the sputtering source power is larger in the embodiment 11 than in the first embodiment, and the reaction source power is larger in the embodiment 14 than in the first embodiment.
  • the results show that better results can be obtained by using the sputtering parameters of Example 1 under this system.
  • Examples 15-17 compared with Example 1, increase the definition of the substrate temperature and the definition of the annealing process, which can be advantageous for improving the refractive index and stability.
  • Figure 4 shows the effect of the ratio of oxygen to hydrogen-oxygen mixed gas at 850 nm on the refractive index and extinction coefficient of the silicon oxyhydroxide film.
  • the effect of the ratio of oxygen to the hydrogen-oxygen mixed gas on the refractive index and extinction coefficient of the silicon oxyhydroxide film at 850 nm is similar to that at 940 nm.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film comprises the following steps:
  • the reaction source is turned on, the power of the reaction source is 3 KW, and the reaction source region is supplied with hydrogen, nitrogen, and argon gas, and the gas flow rate is adjusted so that the volume of nitrogen passing through the sum of hydrogen and nitrogen is 5%, and the gas is excited.
  • the plasma is formed, and the substrate is moved at a high speed under the action of an electric field, and finally reacts with the silicon film on the substrate to form a nitrogen-containing silicon hydride film.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film wherein the volume percentage of nitrogen gas in the step (e) is 8%, and the remaining steps and parameters are the same as in the embodiment 15.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film wherein the volume percentage of nitrogen gas in the step (e) is 12%, and the remaining steps and parameters are the same as in the embodiment 15.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film wherein the volume percentage of nitrogen gas in the step (e) is 20%, and the remaining steps and parameters are the same as in the embodiment 15.
  • step (e) A method for preparing a high refractive index nitrogen-containing silicon hydride film, wherein the reaction source power in step (e) is 1.5 KW, and the remaining steps and parameters are the same as in the embodiment 15.
  • step (e) A method for preparing a high refractive index nitrogen-containing silicon hydride film, wherein the reaction source power in step (e) is 5 KW, and the remaining steps and parameters are the same as in the embodiment 15.
  • step (e) A method for preparing a high refractive index nitrogen-containing silicon hydride film, wherein the reaction source power in step (e) is 10 KW, and the remaining steps and parameters are the same as in the embodiment 15.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film comprises the following steps:
  • the power of the reaction source is 2KW, and the reaction source area is supplied with hydrogen, nitrogen and argon gas to adjust the gas flow rate so that the nitrogen gas accounts for 6% by volume of the sum of hydrogen and nitrogen, hydrogen and nitrogen.
  • the gas After being uniformly mixed with the argon gas in the gas mixing chamber, the gas is excited to form a plasma, and moves to the substrate at a high speed under the action of the electric field, and finally reacts with the silicon film on the substrate to form a nitrogen-containing silicon hydride film.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film comprises the following steps:
  • the power of the reaction source is 2KW, and the reaction source area is supplied with hydrogen, nitrogen and argon gas to adjust the gas flow rate so that the nitrogen gas accounts for 6% by volume of the sum of hydrogen and nitrogen, hydrogen and nitrogen.
  • the gas After being uniformly mixed with the argon gas in the gas mixing chamber, the gas is excited to form a plasma, and moves to the substrate at a high speed under the action of the electric field, and finally reacts with the silicon film on the substrate to form a nitrogen-containing silicon hydride film.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film comprises the following steps:
  • the power of the reaction source is 2KW, and the reaction source area is supplied with hydrogen, nitrogen and argon gas to adjust the gas flow rate so that the nitrogen gas accounts for 6% by volume of the sum of hydrogen and nitrogen, hydrogen and nitrogen.
  • the gas After being uniformly mixed with the argon gas in the gas mixing chamber, the gas is excited to form a plasma, and moves to the substrate at a high speed under the action of the electric field, and finally reacts with the silicon film on the substrate to form a nitrogen-containing silicon hydride film.
  • a method for preparing a high refractive index nitrogen-containing silicon hydride film wherein the volume percentage of nitrogen gas in the step (e) is 23%, and the remaining steps and parameters are the same as in the embodiment 22.
  • the oxygen-containing silicon hydride film obtained by the method of the present invention (nitrogen-to-hydrogen-nitrogen mixed gas ratio of 5 to 20%) has a refractive index of 3.0-3.3 at 940 nm, and a high refractive index and a small absorption can be obtained. Film.
  • Figure 5 shows the effect of the ratio of nitrogen to hydrogen-nitrogen mixed gas at 940 nm on the refractive index and extinction coefficient of the silicon oxyhydroxide film.
  • the ratio of nitrogen to hydrogen-nitrogen mixed gas has an effect on the refractive index and extinction coefficient of the nitrogen-containing silicon hydride film.
  • the proportion of nitrogen increases, the refractive index of the silicon hydride film decreases, and the extinction coefficient gradually rises.
  • the proportion of nitrogen exceeds 20%, the extinction coefficient increases significantly.
  • Example 2 Comparative Example 2 Compared with Example 18, the nitrogen gas accounted for 23% by volume of the sum of hydrogen and nitrogen gas. Although the refractive index was higher, the extinction coefficient was also higher, which was not satisfactory.
  • Example 22 and Example 23 compared with Example 18, although the reaction source power is different, the refractive index and the extinction coefficient are not much different.
  • Example 24 compared with Example 18, the reaction source power is large, and the result indicates that A better effect can be obtained by using the sputtering parameters of Example 1 under the sputtering system.
  • Example 25 increases the definition of the substrate temperature and the definition of the annealing process, which can contribute to the improvement of stability.
  • a filter stack comprising a plurality of high refractive index silicon oxyhydroxide films of Embodiment 3 and a plurality of SiO 2 films, wherein a plurality of high refractive index silicon hydride films of Embodiment 3 and a plurality of SiO 2 films are alternately stacked.
  • the high refractive index silicon hydride film of Example 3 had a thickness of 100 nm
  • the SiO 2 film had a thickness of 200 nm
  • the filter laminate had a thickness of 5 ⁇ m.
  • a filter stack comprising a plurality of high refractive index nitrogen-containing silicon hydride films of Example 17 and a plurality of low refractive index silicon oxyhydroxide films (Example 7), alternately stacked, high refractive index nitrogen-containing hydrogenation
  • the thickness of the silicon film was 100 nm
  • the thickness of the low refractive index silicon oxyhydroxide film was 100 nm
  • the thickness of the filter laminate was 3 ⁇ m.
  • the measured spectral curve of the 0-40° incident of a 940 nm center wavelength bandpass plated using a TiO 2 filter stack is shown in FIG.
  • a 940 nm band-pass filter is designed using a conventional high refractive index such as TiO 2 , Ta 2 O 5 , or Nb 2 O 5 , and its center wavelength is largely shifted with angle (about 30 nm), and the total thickness of the film system is thick (this is 2-3 times the thickness of the invention means that the production efficiency is low.
  • the filter coated with the material of the present invention has better spectral characteristics than is known.
  • the sputtering process and the reaction process of the preparation method of the high refractive index hydrogenated silicon film of the present invention are separate and relatively independent, and the target of the sputtering process is not easily contaminated by the reaction gas, thereby effectively avoiding the poisoning problem of the target. This method improves production efficiency and reduces costs.
  • the obtained oxygen- or nitrogen-containing silicon hydride film has a higher refractive index and lower absorption.
  • the hydrogenated silicon film obtained by the method for producing a high refractive index hydrogenated silicon film of the present invention has a high refractive index and low absorption.
  • the filter stack of the present invention is obtained by using the oxygen-containing or nitrogen-containing silicon hydride film as a high refractive index material, has a high transmittance, and has a small central wavelength shift amount and a small signal loss. The signal to noise ratio is superior.
  • the filter of the present invention comprises the above-described filter stack, and thus has the same advantages as the above-described filter stack, so that the produced filter has a high transmittance and a central wavelength shift amount. small.

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Abstract

一种高折射率氢化硅薄膜的制备方法、高折射率氢化硅薄膜、滤光叠层和滤光片,涉及光学薄膜技术领域。该制备方法包括以下步骤:(a)通过磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;(b)硅薄膜在含有活性氢和活性氧的环境中形成含氧的氢化硅薄膜,活性氧的数量占活性氢和活性氧总数量的4~99%,或,硅薄膜在含有活性氢和活性氮的环境中形成含氮的氢化硅薄膜,活性氮的数量占活性氢和活性氮总数量的5~20%。该制备方法将溅射与反应分开进行,先通过磁控Si靶溅射,在基体上沉积Si,再通过活性氢和活性氧/氮的等离子体与硅发生反应获得含氧或含氮SiH,不仅避免靶材中毒问题,而且SiH薄膜具有较高的折射率和较低的吸收。

Description

高折射率氢化硅薄膜的制备方法、高折射率氢化硅薄膜、滤光叠层和滤光片
相关申请的交叉引用
本申请要求于2017年11月01日提交中国专利局的申请号为2017110611306、名称为“高折射率氢化硅薄膜的制备方法、高折射率氢化硅薄膜、滤光叠层和滤光片”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
技术领域
本发明涉及光学薄膜技术领域,具体而言,涉及一种高折射率氢化硅薄膜的制备方法、高折射率氢化硅薄膜、滤光叠层和滤光片。
背景技术
氢化硅薄膜由于在红外成像传感器、太阳能电池及薄膜晶体管等微电子器件中有着广泛应用前景而备受关注。氢化硅的制备工艺主要分为化学沉积法,如等离子体增强化学气相沉积等;物理沉积法,如射频溅射等。
在3D等近红外成像系统中,会用到一种窄带带通滤光片,要求即使光线大角度入射,其中心波长随角度偏移量尽量的小,这样才能保证在一个较广的视场角内信号损失少、信噪比高。而制作这样的窄带带通滤光片,需要用到超高折射率的镀膜材料和较低折射率的相互叠加镀制而成,一般的膜系结构在几十层甚至到上百层,总厚度超过8μm。
现有技术中JDS优尼弗思公司在2013年申请的公开号为CN 104471449 A的中国专利中提到一种高折射率、低消光系数氢化硅,结果显示每个氢化硅层在800nm至1100nm波长范围内的折射率均大于3,在800nm至1100nm波长范围内的消光系数均小于0.0005。这种高折射率的氢化硅层是在该公司具有专利的镀膜设备(溅射沉积系统)上实现的,溅射沉积系统结构如图1所示。溅射沉积系统通过等离子体激发源(PAS)460对通入的氢气进行活化,与溅射的硅材料(硅靶)431重叠,使氢化硅层以相对较高的沉积速率和相对较低的氢含量被沉积到基底420上。该技术属于反应溅射,即在反应气体的环境下溅射靶材(硅靶)时,靶材与气体发生反应形成化合物——氢化硅。而这种技术采用反应溅射原理,可能存在靶材“中毒”的情况,即靶材容易被氢气污染,造成生产不稳定等问题。
为制作具有低偏效应的滤光片,一般的溅射设备难以制备超过2.5以上的高折射率、低于0.0005的消光系数的氢化硅,必须使用复杂的、专用的镀膜设备。而利用现有技术制作的镀膜机,其生产效率较低,这就造成单片的成本高居不下。
有鉴于此,特提出本发明。
发明内容
本发明的目的之一在于提供一种高折射率氢化硅薄膜的制备方法,该方法使生产效率得到提升,降低了成本,获得的含氧或含氮的氢化硅薄膜具有较高的折射率和更低的吸收。
本发明的目的之二在于提供一种采用所述的高折射率氢化硅薄膜的制备方法得到的高折射率氢化硅薄膜,该薄膜折射率高、吸收低。
本发明的目的之三在于提供一种滤光叠层,以所述含氧或含氮的氢化硅薄膜作为高折射率材料制得,其透过率高,且具有中心波长偏移量较小,信号损失少、信噪比高等优势。
本发明的目的之四在于提供一种包含所述滤光叠层的滤光片,该滤光片具有与上述滤光叠层相同的优势,使得制成的滤光片具有较高的透过率且中心波长偏移量小。
为了实现本发明的上述目的,特采用以下技术方案:
第一方面,提供了一种高折射率氢化硅薄膜的制备方法,包括以下步骤:
(a)通过磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)硅薄膜在含有活性氢和活性氧的环境中形成含氧的氢化硅薄膜,活性氧的数量占活性氢和活性氧总数量的4~99%,或,
硅薄膜在含有活性氢和活性氮的环境中形成含氮的氢化硅薄膜,活性氮的数量占活性氢和活性氮总数量的5~20%。
优选地,在本发明技术方案的基础上,步骤(b)中活性氧的数量占活性氢和活性氧总数量的4~70%,或,活性氮的数量占活性氢和活性氮总数量的5~18%。
优选地,步骤(b)中活性氧的数量占活性氢和活性氧总数量的5~20%,或,活性氮的数量占活性氢和活性氮总数量的5~10%。
优选地,在本发明技术方案的基础上,高折射率氢化硅薄膜的制备方法包括以下步骤:
(a)在存在惰性气体的条件下通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)在存在氢气、氧气和惰性气体混合气体的条件下通过RF或ICP对混合气体活化,形成等离子体,等离子体与硅薄膜反应,形成含氧的氢化硅薄膜,其中,氧气占氢气和氧气混合气体的体积百分比为4~99%,优选4~70%,进一步优选5~20%,或,
在存在氢气、氮气和惰性气体混合气体的条件下通过RF或ICP对混合气体活化,形成等离子体,等离子体与硅薄膜反应,形成含氮的氢化硅薄膜,其中,氮气占氢气和氮气混合气体的体积百分比为5~20%,优选5~18%,进一步优选5~10%。
优选地,在本发明技术方案的基础上,步骤(a)中Si靶溅射功率为额定功率的5%-80%,优选20%-80%,进一步优选40%-80%,进一步优选40%-70%,进一步优选50%-70%;和/或,步骤(b)中通过RF或ICP对混合气体活化的功率为额定功率的5%-80%,优选5%-50%,进一步优选15%-50%,进一步优选20%-50%。
优选地,一种典型的高折射率氢化硅薄膜的制备方法包括以下步骤:
(a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氧气和氩气,形成等离子体,与硅薄膜发生反应,形成含氧的氢化硅薄膜,反应源为RF或ICP等离子体激发源;
其中,溅射源的功率为额定功率的5%-80%,反应源的功率为额定功率的5%-80%,通入的氧气占通入氢气和氧气总和的体积百分比为4~99%。
优选地,另一种典型的高折射率氢化硅薄膜的制备方法包括以下步骤:
(a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氮气和氩气,形成等离子体,与硅薄膜发生反应,形成含氮的氢化硅薄膜,反应源为RF或ICP等离子体激发源;
其中,溅射源的功率为额定功率的5%-80%,反应源的功率为额定功率的5%-80%,通入的氮气占通入氢气和氮气总和的体积百分比为5~20%。
优选地,在本发明技术方案的基础上,转动机构选自转盘、滚筒、转架杆中的一种。
优选地,在本发明技术方案的基础上,镀膜腔室设置有用于将镀膜腔室分割为第一腔室和第二腔室的挡板,溅射源位于第一腔室内,反应源位于第二腔室内。
优选地,在本发明技术方案的基础上,镀膜腔室设置有气体混合腔,氢气、氧气和氩气分别通入气体混合腔,混合均匀后通入镀膜腔室进行活化;或,
氢气、氮气和氩气分别通入气体混合腔,混合均匀后通入镀膜腔室进行活化。
优选地,在本发明技术方案的基础上,在步骤(a)中,在开启溅射源之前,还包括 加热基体至基体温度为100-300℃,接着通入氩气对镀膜腔室和基体进行轰击清洗;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至高于10 -3Pa;
优选地,轰击清洗的时间为1~5min,轰击功率为额定功率的5%-80%。
优选地,在本发明技术方案的基础上,在步骤(b)结束后,还包括将含氧的氢化硅薄膜或含氮的氢化硅薄膜在退火炉内100-300℃退火60-180min。
优选地,在本发明技术方案的基础上,对含氧的氢化硅薄膜或含氮的氢化硅薄膜在退火炉内退火包括:
以升温速率为1-15℃/min的速度升温至100-300℃,时间为30-60min;
接着保持恒温在100-300℃,时间为30-120min;
接着以降温速度为10-30℃/min的速度降温至室温。
第二方面,提供了一种采用上述高折射率氢化硅薄膜的制备方法得到的高折射率氢化硅薄膜,所述高折射率氢化硅薄膜在800~1100nm波长范围内的折射率为1.46~3.7,所述高折射率氢化硅薄膜在800~1100nm波长范围内的消光系数小于0.0001。
第三方面,提供了一种滤光叠层,包括多个上述高折射率氢化硅薄膜和多个低折射率薄膜,多个高折射率氢化硅薄膜和多个低折射率薄膜交替堆叠,其中,所述低折射率薄膜为在800~1100nm波长范围内折射率小于所述高折射率氢化硅薄膜在800~1100nm波长范围内折射率的薄膜。
优选地,在本发明技术方案的基础上,所述低折射率薄膜为二氧化硅薄膜;
优选地,所述低折射率薄膜为低折射率氢化硅薄膜,所述低折射率薄膜为在800~1100nm波长范围内折射率小于所述高折射率氢化硅薄膜在800~1100nm波长范围内折射率的薄膜;
优选地,滤光叠层的层数为10~100层;
优选地,滤光叠层的厚度为1~10μm。
第四方面,提供了一种滤光片,其包含上述滤光叠层。
与已有技术相比,本发明具有如下有益效果:
(1)本发明高折射率氢化硅薄膜的制备方法首先利用磁控溅射法,磁控Si靶溅射,在基体上沉积Si,形成硅薄膜,然后在含有活性氢的环境中通过氢化反应形成氢化硅薄膜,溅射过程和反应过程是分开的,相对独立的,溅射过程靶材不易被反应气体污染,有效避免靶材中毒问题。同时,在含有活性氢的环境中加入特定比例的活性氧或活性氮,在氢化反应的同时发生氧化反应或氮化反应,形成高折射率、低吸收的含氧氢化硅薄膜或含氮氢化硅薄膜,此外,通过该方法使生产效率得到提升,降低了成本。
(2)本发明高折射率氢化硅薄膜的制备方法得到的氢化硅薄膜在800~1100nm波长范围内的折射率为1.46~3.7,在800~1100nm波长范围内的消光系数小于0.0001,其薄膜折射率高,吸收低。
(3)本发明的滤光叠层以所述含氧或含氮的氢化硅薄膜作为高折射率材料,与诸如氧化硅、高含氧的氢化硅等低于上述折射率的较低折射率材料交替堆叠,形成高透射率的滤光叠层,滤光叠层镀制在玻璃、树脂基板之上,形成光学干涉薄膜带通、长波通、短波通等滤光片,使光线在大角度入射时滤光片的中心波长偏移量较小,进而使传感器在大视场角范围内具有信号损失少、信噪比高等优势,可应用在夜视,3D成像、3D建模、人脸识别、虹膜识别、手势识别等所有需要低偏移效应的滤光器、传感器系统中。
(4)本发明的滤光片,包含了上述滤光叠层,因此具有与上述滤光叠层相同的优势,使得制成的滤光片具有较高的透过率且中心波长偏移量小。
附图说明
图1为现有技术溅射沉积系统的结构示意图;
图2为本发明一种实施方式的真空溅射反应镀膜系统的结构示意图;
图3为940nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜折射率和消光系数的影响((a)为940nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜折射率的影响,(b)为940nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜消光系数的影响);
图4为850nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜折射率和消光系数的影响((a)为940nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜折射率的影响,(b)为940nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜消光系数的影响);
图5为940nm下氮气占氢氮混合气体的比例对含氮氢化硅薄膜折射率和消光系数的影响((a)为940nm下氮气占氢氮混合气体的比例对含氮氢化硅薄膜折射率的影响,(b)为940nm下氮气占氢氮混合气体的比例对含氮氢化硅薄膜消光系数的影响);
图6为使用实施例28的滤光叠层镀制的940nm中心波长的带通滤光片0-30°入射的实测光谱曲线;
图7为使用实施例28的滤光叠层镀制的850nm中心波长的带通滤光片0-30°入射的实测光谱曲线;
图8为使用实施例29的滤光叠层镀制的940nm中心波长的带通滤光片0-30°入射的实测光谱曲线;
图9为使用TiO 2滤光叠层镀制的940nm中心波长的带通滤光片0-30°入射的实测光谱曲线。
附图标记:100-基片;200-转动机构;300-溅射源;400-反应源;500-镀膜腔室;600-挡板;700-气体混合腔。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
根据本发明的第一个方面,提供了一种高折射率氢化硅薄膜的制备方法,包括以下步骤:
(a)通过磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)硅薄膜在含有活性氢和活性氧的环境中形成含氧的氢化硅薄膜,活性氧的数量占活性氢和活性氧总数量的4~99%,或,
硅薄膜在含有活性氢和活性氮的环境中形成含氮的氢化硅薄膜,活性氮的数量占活性氢和活性氮总数量的5~20%。
步骤(a)中,Si靶上为单晶或多晶形态的半导体高纯硅材料。
典型但非限制性的基体例如为单晶Si片、玻璃片或树脂片。
首先利用磁控溅射法,磁控Si靶溅射,在基体上沉积Si,形成硅薄膜。
磁控溅射是物理气相沉积(Physical Vapor Deposition,PVD)的一种,具有设备简单、易于控制、镀膜面积大和附着力强等优点。磁控溅射可以在真空镀溅射镀膜机中进行,Si靶安装在中频(MF,Medium Frequency)或射频(RF,Radio Frequency)阴极上,真空室内通入惰性气体(典型但非限制性的例如氩气),氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上,形成硅薄膜。
步骤(b)中,活性氢可以通过活化氢气获得,活性氢的原子和分子形式均被认为存在于等离子体中,活性氢更具化学活性,因此可与Si生成Si-H键。
同理活性氧可以通过活化氧气获得,可生成Si-O键,活性氮可以通过活化氮气获得,可生成Si-N键。
优选可以通过射频(RF)或ICP((Inductive Coupled Plasma Emission Spectrometer,电 感耦合等离子体)等离子体激发源激发氢气和氧气,或者,激发氢气和氮气,以获得活性氢和活性氧,或者,活性氢和活性氮,从而与硅反应得到含氧的氢化硅或含氮的氢化硅。
氢化硅中含氧量或含氮量对薄膜的折射率和吸收具有重要影响,为了获得高折射率和吸收小的氢化硅薄膜,需要控制氢化硅中含氧量或含氮量。
步骤(b)中,当硅薄膜在含有活性氢和活性氧的环境中形成含氧的氢化硅薄膜时,控制活性氧的数量占活性氢和活性氧总数量的4~99%,例如4%、5%、10%、20%、30%、40%、50%、60%、70%、80%、90%、95%和99%中的一者或任意两者之间的范围值。
步骤(b)中,当硅薄膜在含有活性氢和活性氮的环境中形成含氮的氢化硅薄膜,控制活性氮的数量占活性氢和活性氮总数量的5~20%,例如5%、6%、8%、10%、12%、14%、15%、16%、18%和20%中的一者或任意两者之间的范围值。
通过调节活性氧在活性氢和活性氧中的占比,从而控制含氧的氢化硅薄膜的含氧量,可以获得800-1100nm的折射率1.46-3.7、消光系数小于0.0001的高折射率、低吸收的氢化硅薄膜。通过调节活性氮在活性氢和活性氮中的占比,从而控制含氮的氢化硅薄膜的含氮量,可以获得800-1100nm的折射率3.0-3.3、消光系数小于0.0001的高折射率、低吸收的氢化硅薄膜。
活性氧/氮含量过低,不好控制,当活性氮含量过高时,虽然折射率相对比较高,但是消光系数较大,不能获得需要的膜层。
形成硅薄膜后通过氢化反应获得氢化硅薄膜,并且在氢化反应的同时发生一定量的氧化反应或氮化反应,形成高折射率、低吸收的含氧氢化硅薄膜或含氮氢化硅薄膜。
优选地,该过程可以与上述步骤(a)过程在同一真空镀溅射镀膜机中进行,但需要注意的是两个过程是独立分开进行的。
现有技术中获得氢化硅的方法是通过反应溅射方式,溅射与反应是同时进行的,在反应气体的环境下溅射靶材,靶材容易被氢气污染,造成生产不稳定等问题。
本发明中采用挡板将镀膜腔室分割为第一腔室和第二腔室,溅射源位于第一腔室内,反应源位于第二腔室内。本实施例中的分割并非完全独立和密封,转动机构上的基片通过转动机构的转动带动基片进入第一腔室进行溅射,溅射完成后进入第二腔室与混合气体进行反应。本发明中通过挡板对溅射源和反应源进行物理上的区分,同时在设置溅射源和反应源的位置时,尽可能的扩大溅射源和反应源的位置距离,实现相对独立,溅射过程靶材不易被反应气体污染,有效避免靶材中毒问题。
本发明的制备方法首先利用磁控溅射法,磁控Si靶溅射,在基体上沉积Si,形成硅薄膜,然后在含有活性氢的环境中通过氢化反应形成氢化硅薄膜,溅射过程和反应过程是分开的,相对独立的,溅射过程靶材不易被反应气体污染,有效避免靶材中毒问题。同时,在含有活性氢的环境中加入特定比例的活性氧或活性氮,在氢化反应的同时发生氧化反应或氮化反应,形成含氧氢化硅薄膜或含氮氢化硅薄膜,该含氧氢化硅薄膜或含氮氢化硅薄膜具有较高的折射率和更低的吸收。此外,该方法在常规简单的真空溅射镀膜设备或系统即可实现,使生产效率得到提升,降低了生产成本。
优选地,步骤(b)中活性氧的数量占活性氢和活性氧总数量的4~70%,或,活性氮的数量占活性氢和活性氮总数量的5~18%。
进一步优选地,步骤(b)中活性氧的数量占活性氢和活性氧总数量的5~20%,或,活性氮的数量占活性氢和活性氮总数量的5~10%。
通过进一步优化活性氧/活性氮在活性氢和活性氧/活性氮中的占比,从而控制氢化硅的含氧量/含氮量,具有较低含氧量/含氮量的氢化硅薄膜具有更高的折射率和更低的吸收。
在一种优选的实施方式中,高折射率氢化硅薄膜的制备方法包括以下步骤:
(a)在存在惰性气体的条件下通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)在存在氢气、氧气和惰性气体混合气体的条件下通过RF或ICP对混合气体活化, 形成等离子体,等离子体与硅薄膜反应,形成含氧的氢化硅薄膜,其中,氧气占氢气和氧气混合气体的体积百分比为4~99%,优选4~70%,进一步优选5~20%,或,
在存在氢气、氮气和惰性气体混合气体的条件下通过RF或ICP对混合气体活化,形成等离子体,等离子体与硅薄膜反应,形成含氮的氢化硅薄膜,其中,氮气占氢气和氮气混合气体的体积百分比为5~20%,优选5~18%,进一步优选5~10%。
典型但非限制性的惰性气体为氩气。
该步骤可以在真空溅射反应镀膜机内进行,使用例如氩气的等离子体对单晶或多晶形态的半导体硅材料做溅射,使硅材料以纳米级尺寸被溅射到玻璃基片上。再使用具有ICP或RF功能的反应源,通以不同比例的氢气、氧气和氩气混合气体或氢气、氮气和氩气混合气体形成等离子体,对硅材料做氢氧化或氢氮化处理,最终形成一定含量的含氧或含氮的氢化硅薄膜。
其中,镀膜腔室设置有气体混合腔,氢气、氧气和氩气分别通入气体混合腔,混合均匀后通入镀膜腔室进行活化;或,氢气、氮气和氩气分别通入气体混合腔,混合均匀后通入镀膜腔室进行活化。本发明通过设置气体混合腔能够将氢气、氧气和氩气分散混合均匀,从而在利用RF或ICP对混合气体进行活化时,效果更佳,避免未经混合,直接通入氢气、氧气和氩气而导致的活化效果不均一的情况发生。
当通入氢气、氧气和惰性气体混合气体时,氧气占氢气和氧气混合气体的体积百分比为4~99%,例如4%、5%、10%、20%、30%、40%、50%、60%、70%、80%、90%、95%和99%中的任一者或者任意两者之间的范围值,例如优选4~70%,进一步例如优选5~20%。
当通入氢气、氮气和惰性气体混合气体时,氮气占氢气和氮气混合气体的体积百分比为5~20%,例如5%、6%、8%、10%、12%、14%、15%、16%、18%和20%中的任一者或者任意两者之间的范围值,例如优选5~18%,进一步例如优选5~10%。
通入的氧气或氮气过低,不好控制,当氮气体积过高时,虽然折射率相对比较高,但是消光系数较大,不能获得需要的膜层。
在镀制高折射率的氢化硅薄膜时充入了少量的氧气或氮气,从而降低了膜层的消光系数,进而可以提高膜层的透过率。
在一种优选的实施方式中,步骤(a)中Si靶溅射功率为额定功率的5%-80%,优选20%-80%,进一步优选40%-80%,进一步优选40%-70%,进一步优选50%-70%。
Si靶溅射的额定功率例如为15KW,此时步骤(a)中Si靶溅射功率典型但非限制性的例如为0.75KW、1.5KW、3KW、6KW、7KW、8KW、9KW、10KW、11KW和12KW中的任一者或者任意两者之间的范围值。
在一种优选的实施方式中,步骤(b)中通过RF或ICP对混合气体活化的功率为额定功率的5%-80%,优选5%-50%,进一步优选15%-50%,进一步优选20%-50%。
通过RF或ICP对混合气体活化的功率典型的指具有ICP或RF功能的反应源功率,反应源功率的额定功率例如为10KW,此时反应源功率典型但非限制性的例如为0.5KW、1KW、2KW、3KW、4KW、5KW、6KW、7KW和8KW中的任一者或者任意两者之间的范围值。
通过调整溅射功率和反应功率对薄膜折射率和吸收也会有一定影响,因此,要获得高折射率和吸收小的薄膜,还需要配合调整相应的溅射功率和反应功率等参数,需要注意的是,不同机台的参数具体数值可能会稍有不同,根据实际情况调整即可。
优选地,一种典型的高折射率含氧的氢化硅薄膜的制备方法包括以下步骤:
(a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氧气和氩气,形成等离子体,与硅薄膜发生反应,形成含氧的氢化硅薄膜,反应源为RF或ICP等离子 体激发源;
其中,溅射源的功率为额定功率的5%-80%,反应源的功率为额定功率的5%-80%,通入的氧气占通入氢气和氧气总和的体积百分比为4~99%。
溅射源的额定功率例如为15KW,此时溅射源的功率典型但非限制性的例如为0.75KW、1.5KW、3KW、6KW、7KW、8KW、9KW、10KW、11KW和12KW中的任一者或者任意两者之间的范围值,反应源的额定功率例如为10KW,此时反应源的功率典型但非限制性的例如为0.5KW、1KW、2KW、3KW、4KW、5KW、6KW、7KW和8KW中的任一者或者任意两者之间的范围值,通入的氧气占通入氢气和氧气总和的体积百分比例如为4%、5%、10%、20%、30%、40%、50%、60%、70%、80%、90%、95%和99%中的任一者或者任意两者之间的范围值。
通入的氧气占通入氢气和氧气混合气体的体积百分比可以通过调节各气体流量(sccm)实现。
进一步地,一种典型的高折射率含氧的氢化硅薄膜的制备方法包括以下步骤:
(a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,加热基体至基体温度为100-300℃,接着通入氩气对镀膜腔室和基体进行轰击清洗;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至高于10 -3Pa;开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氧气和氩气,形成等离子体,与硅薄膜发生反应,形成含氧的氢化硅薄膜,反应源为RF或ICP等离子体激发源;
(c)将含氧的氢化硅薄膜在退火炉内100-300℃退火60-180min。具体地,以升温速率为1-15℃/min的速度升温至100-300℃,时间为30-60min;接着保持恒温在100-300℃,时间为30-120min;接着以降温速度为10-30℃/min的速度降温至室温,取出。其中,轰击清洗的时间为1~5min,轰击功率为额定功率的5%-80%。
本发明中以特定的退火工艺和参数对含氧的氢化硅薄膜进行退火处理,限定特定的升温速度、降温速度、退火时间等参数,有利于提高其结构和光学特性显示出较好的热稳定性。优选地,一种典型的高折射率含氮的氢化硅薄膜的制备方法包括以下步骤:
(a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氮气和氩气,形成等离子体,与硅薄膜发生反应,形成含氮的氢化硅薄膜,反应源为RF或ICP等离子体激发源;
其中,溅射源的功率为额定功率的5%-80%,反应源的功率为额定功率的5%-80%,通入的氮气占通入氢气和氮气总和的体积百分比为5~20%。
溅射源的额定功率例如为15KW,此时溅射源的功率典型但非限制性的例如为0.75KW、1.5KW、3KW、6KW、7KW、8KW、9KW、10KW、11KW和12KW中的任一者或者任意两者之间的范围值,反应源的额定功率例如为10KW,此时反应源的功率典型但非限制性的例如为1.5KW、2KW、3KW、4KW、5KW、6KW、7KW和8KW中的任一者或者任意两者之间的范围值,通入的氮气占通入氢气和氮气总和的体积百分比例如为5%、6%、8%、10%、12%、14%、15%、16%、18%和20%中的任一者或者任意两者之间的范围值。
通入的氮气占通入氢气和氮气混合气体的体积百分比可以通过调节各气体流量(sccm)实现。
进一步地,一种典型的高折射率含氮的氢化硅薄膜的制备方法包括以下步骤:
(a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,加热基体至基体温度为100-300℃,接着通入氩气对镀膜腔室和基体进行轰击清洗;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至高于10 -3Pa;开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
(b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氮气和氩气,形成等离子体,与硅薄膜发生反应,形成含氮的氢化硅薄膜,反应源为RF或ICP等离子体激发源;
(c)将含氮的氢化硅薄膜在退火炉内100-300℃退火60-180min。具体地,以升温速率为1-15℃/min的速度升温至100-300℃,时间为30-60min;接着保持恒温在100-300℃,时间为30-120min;接着以降温速度为10-30℃/min的速度降温至室温,取出。其中,轰击清洗的时间为1~5min,轰击功率为额定功率的5%-80%。轰击的额定功率例如为10KW,此时,在本实施方案中,轰击功率例如可以为0.5-8KW。
本发明中以特定的退火工艺和参数对含氮的氢化硅薄膜进行退火处理,限定特定的升温速度、降温速度、退火时间等参数,有利于提高其结构和光学特性显示出较好的热稳定性。该典型的含氧的氢化硅薄膜或含氮的氢化硅薄膜的制备方法可以在真空溅射反应镀膜系统中进行,图2为本发明一种实施方式的真空溅射反应镀膜系统的结构示意图。
结合图2说明含氧的氢化硅薄膜的制备过程:
A.干净的基片100放在转动机构200上,镀膜面朝向靶材;
B.转动机构200在镀膜腔室500内匀速旋转;
C.当真空度在高于10 -3Pa时,加热基体至基体温度为100-300℃,接着通入氩气对镀膜腔室和基体进行轰击清洗;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至高于10 -3Pa;开启位于第一腔室内的溅射源300并通氩气,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片100上;
D.随着转动机构200的转动,基片100被带往位于第二腔室内的反应源(RF/ICP)区域,溅射源300和反应源400被隔板600间隔开;
E.反应源400区域通入氢气、氧气和氩气,氢气、氧气和氩气在气体混合腔室700内混合均匀后排出,形成等离子体,在电场的作用下向基片100高速运动,最终与基片100上的硅薄膜发生反应,化合成含氧的氢化硅薄膜。
F.将含氧的氢化硅薄膜在退火炉内以升温速率为1-15℃/min的速度升温至100-300℃,时间为30-60min;接着保持恒温在100-300℃,时间为30-120min;接着以降温速度为10-30℃/min的速度降温至室温,取出。溅射源的功率参数范围为额定功率的5%-80%,反应源的功率参数范围为额定功率的5%-80%,通入的氧气占通入氢气和氧气总和的体积百分比为4~99%。轰击清洗的时间为1~5min,轰击功率为额定功率的5%-80%。转动机构200可以选自转盘、滚筒、转架杆中的一种。
结合图2说明含氮的氢化硅薄膜的制备过程:
A.干净的基片100放在转动机构200上,镀膜面朝向靶材;
B.转动机构200在镀膜腔室500内匀速旋转;
C.当真空度在高于10 -3Pa时,加热基体至基体温度为100-300℃,接着通入氩气对镀膜腔室和基体进行轰击清洗;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至高于10 -3Pa;开启位于第一腔室内的溅射源300并通氩气,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片100上;
D.随着转动机构200的转动,基片100被带往位于第二腔室内的反应源(RF/ICP)区域,溅射源300和反应源400被隔板600间隔开;
E.反应源400通以氢气、氮气和氩气,氢气、氮气和氩气在气体混合腔室内混合均匀后排出,形成等离子体,在电场的作用下向基片100高速运动,最终与基片100上的硅薄 膜发生反应,化合成含氮的氢化硅薄膜。
F.将含氮的氢化硅薄膜在退火炉内以升温速率为1-15℃/min的速度升温至100-300℃,时间为30-60min;接着保持恒温在100-300℃,时间为30-120min;接着以降温速度为10-30℃/min的速度降温至室温,取出。
溅射源的功率参数范围为额定功率的5%-80%,反应源的功率参数范围为额定功率的5%-80%,通入的氮气占通入氢气和氮气总和的体积百分比为5~20%。轰击清洗的时间为1~5min,轰击功率为额定功率的5%-80%。转动机构200可以选自转盘、滚筒、转架杆中的一种。
玻璃基片被排列在转动机构球罩上,随转动机构球罩逆时针转动,转速可调,被镀膜的基片先经过溅射源,被沉积一层很薄的硅薄后,旋转到反应源,被由氢氧氩,或氢氮氩离子和电子等组成的等离子体化合成所需特性的光学薄膜。在制备高折射率的薄膜时,反应源充入的混合气体中,通过调节氢气和氧气、氢气和氮气的比例(流量),可以制备800~1100nm的最低折射率从1.46~3.7逐渐变化、消光系数可小于0.0001的薄膜。当反应源充入的气体是氧气占比高的氢、氧和氩的混合气体,或是纯氧气、氢和氩的混合气体,可以制备800~1100nm的折射率从1.46~1.7逐渐变化、消光系数可小于0.0001的薄膜。
需要特别指出的是,反应源的混合气体中氧气或氮气占比是重要参数,并且,如果要获得高折射率、吸收小的薄膜,还需要配合调整相应的溅射功率、反应功率等参数,不同机台的参数具体数值会不相同。
在镀制高折射率的氢化硅薄膜时充入了少量的氧气或氮气,从而降低了膜层的消光系数,进而可以提高多层膜的透过率。
根据本发明的第二个方面,提供了一种采用上述高折射率氢化硅薄膜的制备方法得到的高折射率氢化硅薄膜。
该高折射率氢化硅薄膜在800~1100nm波长范围内的折射率为1.46~3.7,该高折射率氢化硅薄膜在800~1100nm波长范围内的消光系数小于0.0001。
根据本发明的第三个方面,提供了一种滤光叠层,包括多个上述高折射率氢化硅薄膜和多个低折射率薄膜,多个高折射率氢化硅薄膜和多个低折射率薄膜交替堆叠。
低折射率薄膜指在800~1100nm波长范围内折射率小于本发明高折射率氢化硅薄膜在800~1100nm波长范围内折射率的薄膜。
在一种优选的实施方式中,低折射率薄膜为二氧化硅薄膜。
二氧化硅薄膜的折射率一般在1.46-1.50之间,属于较低折射率薄膜,与本发明高于此折射率的氢化硅薄膜交替堆叠,构成滤光叠层。
在一种优选的实施方式中,低折射率薄膜为低折射率氢化硅薄膜。
低折射率氢化硅薄膜这里所指的低折射率是一个相对量,指叠层膜系结构中这个氢化硅薄膜的折射率小于本发明高折射率氢化硅薄膜的折射率。例如采用本发明方法得到的氢化硅薄膜的折射率为3,那么低折射率氢化硅薄膜就指折射率低于3的所有氢化硅薄膜,可以是采用常规方法得到的氢化硅薄膜,也可以是采用本发明方法具有高含氧量的氢化硅薄膜。
优选地,滤光叠层的层数为10~100层;
优选地,滤光叠层的厚度为1~10μm。
滤光叠层包括用作高折射率层的多个氢化硅薄膜和多个低折射率层,多个氢化硅薄膜与多个低折射率层交替堆叠。通常,滤光叠层可以由以(高/低)n、(高/低)n高或低(高/低)n顺序堆叠的多个氢化硅层和多个低折射率层组成。通常,滤光叠层总共包括10至100层,即5≤n≤50。同样在通常情况下,每个氢化硅层和低折射率层的厚度在3~300nm之间,滤光叠层的厚度为1~10μm。一般而言,层数和厚度根据具体光学设计进行选择。
根据本发明的第四个方面,提供了一种包含上述滤光叠层的滤光片。
典型但非限制性的滤光片例如为带通、长波通或短波通滤光片。
本发明的滤光叠层以所述含氧或含氮的氢化硅薄膜作为高折射率材料,与诸如氧化硅、高含氧的氢化硅等低于上述折射率的较低折射率材料交替堆叠,形成高透射率的滤光叠层,滤光叠层镀制在玻璃、树脂基板之上,形成光学干涉薄膜带通、长波通、短波通等滤光片,使光线在大角度入射时滤光片的中心波长偏移量较小,进而使传感器在大视场角范围内具有信号损失少、信噪比高等优势,可应用在夜视,3D成像、3D建模、人脸识别、虹膜识别、手势识别等所有需要低偏移效应的滤光器、传感器系统中。
下面通过具体的实施例和对比例进一步说明本发明,但是,应当理解为,这些实施例仅是用于更详细地说明之用,而不应理解为用于以任何形式限制本发明。本发明涉及的各原料均可通过商购获取。
实施例的高折射率含氧/氮的氢化硅薄膜的制备方法采用光驰科技有限公司NSP1650溅射镀膜系统(如图2所示)实施,基片为玻璃基片。
实施例1
一种高折射率含氧氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)滚筒在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着滚筒的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为2KW,反应源区域通入氢气、氧气和氩气,调节气体流量,使通入氧气占通入氢气和氧气总和的体积百分比为6%,气体被激发形成等离子体,在电场的作用下向基片高速运动,最终与基片上的硅薄膜发生反应,形成含氧的氢化硅薄膜。
实施例2
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中通入氧气占通入氢气和氧气总和的体积百分比为14%,其余步骤和参数与实施例1相同。
实施例3
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中通入氧气占通入氢气和氧气总和的体积百分比为23%,其余步骤和参数与实施例1相同。
实施例4
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中通入氧气占通入氢气和氧气总和的体积百分比为58%,其余步骤和参数与实施例1相同。
实施例5
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中通入氧气占通入氢气和氧气总和的体积百分比为62%,其余步骤和参数与实施例1相同。
实施例6
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中通入氧气占通入氢气和氧气总和的体积百分比为67%,其余步骤和参数与实施例1相同。
实施例7
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中通入氧气占通入氢气和氧气总和的体积百分比为71%,其余步骤和参数与实施例1相同。
实施例8
一种高折射率含氧氢化硅薄膜的制备方法,步骤(c)中溅射源功率为6KW,其余步骤和参数与实施例1相同。
实施例9
一种高折射率含氧氢化硅薄膜的制备方法,步骤(c)中溅射源功率为12KW,其余步 骤和参数与实施例1相同。
实施例10
一种高折射率含氧氢化硅薄膜的制备方法,步骤(c)中溅射源功率为1KW,其余步骤和参数与实施例1相同。
实施例11
一种高折射率含氧氢化硅薄膜的制备方法,步骤(c)中溅射源功率为20KW,其余步骤和参数与实施例1相同。
实施例12
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中反应源功率为0.5KW,其余步骤和参数与实施例1相同。
实施例13
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中反应源功率为5KW,其余步骤和参数与实施例1相同。
实施例14
一种高折射率含氧氢化硅薄膜的制备方法,步骤(e)中反应源功率为10KW,其余步骤和参数与实施例1相同。
实施例15
一种高折射率含氧氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)转盘在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,加热基体至基体温度为160℃,接着通入氩气对镀膜腔室和基体进行轰击清洗,轰击清洗的时间为3min,轰击功率为2.3KW;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至10 -3Pa;开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着转盘的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为2KW,反应源区域通入氢气、氧气和氩气,调节气体流量,使通入氧气占通入氢气和氧气总和的体积百分比为6%,氢气、氧气和氩气在气体混合腔室内混合均匀后排出,气体被激发形成等离子体,在电场的作用下向基片高速运动,最终与基片上的硅薄膜发生反应,形成含氧的氢化硅薄膜。
(f)将含氧的氢化硅薄膜在退火炉内以升温速率为10℃/min的速度升温至200℃,时间为30min;接着保持恒温在200℃,时间为30min;接着以降温速度为15℃/min的速度降温至室温,取出。
实施例16
一种高折射率含氧氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)转盘在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,加热基体至基体温度为100℃,接着通入氩气对镀膜腔室和基体进行轰击清洗,轰击清洗的时间为1min,轰击功率为0.6KW;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至10 -3Pa;开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着转盘的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为2KW,反应源区域通入氢气、氧气和氩气,调节气体流量,使通入氧气占通入氢气和氧气总和的体积百分比为6%,氢气、氧气和氩气在气体混合腔室内混合均匀后排出,气体被激发形成等离子体,在电场的作用下向基片高速运动, 最终与基片上的硅薄膜发生反应,形成含氧的氢化硅薄膜。
(f)将含氧的氢化硅薄膜在退火炉内以升温速率为2℃/min的速度升温至100℃,时间为60min;接着保持恒温在100℃,时间为120min;接着以降温速度为10℃/min的速度降温至室温,取出。
实施例17
一种高折射率含氧氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)转盘在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,加热基体至基体温度为300℃,接着通入氩气对镀膜腔室和基体进行轰击清洗,轰击清洗的时间为5min,轰击功率为4KW;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至10 -3Pa;开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着转盘的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为2KW,反应源区域通入氢气、氧气和氩气,调节气体流量,使通入氧气占通入氢气和氧气总和的体积百分比为6%,氢气、氧气和氩气在气体混合腔室内混合均匀后排出,气体被激发形成等离子体,在电场的作用下向基片高速运动,最终与基片上的硅薄膜发生反应,形成含氧的氢化硅薄膜。
(f)将含氧的氢化硅薄膜在退火炉内以升温速率为15℃/min的速度升温至300℃,时间为40min;接着保持恒温在300℃,时间为80min;接着以降温速度为30℃/min的速度降温至室温,取出。
对比例1
一种二氧化硅薄膜的制备方法,步骤(e)中通入氧气和氩气,不通氢气,其余步骤和参数与实施例1相同,得到二氧化硅薄膜。
试验例1
对实施例1-21以及对比例1方法得到的含氧氢化硅薄膜在940nm进行折射率和消光系数测定,测定方法采用本领域的常规方式测定。
测试结果如表1所示。
表1
Figure PCTCN2018071606-appb-000001
Figure PCTCN2018071606-appb-000002
由表1可以看出,通过采用本发明方法(氧气占氢氧混合气体比例4~99%)得到的含氧氢化硅薄膜在940nm的折射率在1.46-3.7。
图3为940nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜折射率和消光系数的影响。
如图3所示,氧气占氢氧混合气体的比例对含氧氢化硅薄膜折射率和消光系数有影响,随着氧气比例的增大氢化硅薄膜的折射率和消光系数逐渐下降。当氧气占比最大达到100%时,也就是对比例1的情况,这时没有氢气存在,生成的薄膜为二氧化硅薄膜,二氧化硅薄膜具有较低的折射率。
实施例10与实施例1相比,溅射源功率较小,实施例11与实施例1相比,溅射源功率较大,实施例14与实施例1相比,反应源功率较大,结果表明在该系统下采用实施例1的溅射参数能够获得更好的效果。
实施例15-17与实施例1相比,增加了对基体温度的限定以及对退火工艺的限定,能够有利于提升折射率和稳定性。
图4为850nm下氧气占氢氧混合气体的比例对含氧氢化硅薄膜折射率和消光系数的影响。
如图4所示,氧气占氢氧混合气体的比例对含氧氢化硅薄膜在850nm的折射率和消光系数的影响与在940nm下的结果类似。
实施例18
一种高折射率含氮氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)滚筒在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着滚筒的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为3KW,反应源区域通入氢气、氮气和氩气,调节气体流量,使通入氮气占通入氢气和氮气总和的体积百分比为5%,气体被激发形成等离子体,在电场的作用下向基片高速运动,最终与基片上的硅薄膜发生反应,形成含氮的氢化硅薄膜。
实施例19
一种高折射率含氮氢化硅薄膜的制备方法,步骤(e)中通入氮气占通入氢气和氮气总和的体积百分比为8%,其余步骤和参数与实施例15相同。
实施例20
一种高折射率含氮氢化硅薄膜的制备方法,步骤(e)中通入氮气占通入氢气和氮气总和的体积百分比为12%,其余步骤和参数与实施例15相同。
实施例21
一种高折射率含氮氢化硅薄膜的制备方法,步骤(e)中通入氮气占通入氢气和氮气总和的体积百分比为20%,其余步骤和参数与实施例15相同。
实施例22
一种高折射率含氮氢化硅薄膜的制备方法,步骤(e)中反应源功率为1.5KW,其余步骤和参数与实施例15相同。
实施例23
一种高折射率含氮氢化硅薄膜的制备方法,步骤(e)中反应源功率为5KW,其余步骤和参数与实施例15相同。
实施例24
一种高折射率含氮氢化硅薄膜的制备方法,步骤(e)中反应源功率为10KW,其余步骤和参数与实施例15相同。
实施例25
一种高折射率含氮氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)转盘在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,加热基体至基体温度为160℃,接着通入氩气对镀膜腔室和基体进行轰击清洗,轰击清洗的时间为3min,轰击功率为2.3KW;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至10 -3Pa;开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着转盘的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为2KW,反应源区域通入氢气、氮气和氩气,调节气体流量,使通入氮气占通入氢气和氮气总和的体积百分比为6%,氢气、氮气和氩气在气体混合腔室内混合均匀后排出,气体被激发形成等离子体,在电场的作用下向基片高速运动,最终与基片上的硅薄膜发生反应,形成含氮的氢化硅薄膜。
(f)将含氮的氢化硅薄膜在退火炉内以升温速率为10℃/min的速度升温至200℃,时间为30min;接着保持恒温在200℃,时间为30min;接着以降温速度为15℃/min的速度降温至室温,取出。
实施例26
一种高折射率含氮氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)转盘在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,加热基体至基体温度为100℃,接着通入氩气对镀膜腔室和基体进行轰击清洗,轰击清洗的时间为1min,轰击功率为0.6KW;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至10 -3Pa;开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着转盘的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为2KW,反应源区域通入氢气、氮气和氩气,调节气体流量,使通入氮气占通入氢气和氮气总和的体积百分比为6%,氢气、氮气和氩气在气体混合腔室内混合均匀后排出,气体被激发形成等离子体,在电场的作用下向基片高速运动,最终与基片上的硅薄膜发生反应,形成含氮的氢化硅薄膜。
(f)将含氮的氢化硅薄膜在退火炉内以升温速率为2℃/min的速度升温至100℃,时间为60min;接着保持恒温在100℃,时间为120min;接着以降温速度为10℃/min的速度降温至室温,取出。
实施例27
一种高折射率含氮氢化硅薄膜的制备方法,包括以下步骤:
(a)干净的基片放在滚筒上,镀膜面朝向靶材;
(b)转盘在镀膜腔室内匀速旋转;
(c)当真空度高于10 -3Pa时,加热基体至基体温度为300℃,接着通入氩气对镀膜 腔室和基体进行轰击清洗,轰击清洗的时间为5min,轰击功率为4KW;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至10 -3Pa;开启溅射源并通氩气,溅射源功率为8KW,氩气被电离形成等离子体,在电、磁场的作用下轰击高纯硅靶,硅材料被溅射到基片上;
(d)随着转盘的转动,基片被带往反应源区域;
(e)开启反应源,反应源功率为2KW,反应源区域通入氢气、氮气和氩气,调节气体流量,使通入氮气占通入氢气和氮气总和的体积百分比为6%,氢气、氮气和氩气在气体混合腔室内混合均匀后排出,气体被激发形成等离子体,在电场的作用下向基片高速运动,最终与基片上的硅薄膜发生反应,形成含氮的氢化硅薄膜。
(f)将含氮的氢化硅薄膜在退火炉内以升温速率为15℃/min的速度升温至300℃,时间为40min;接着保持恒温在300℃,时间为80min;接着以降温速度为30℃/min的速度降温至室温,取出。
对比例2
一种高折射率含氮氢化硅薄膜的制备方法,步骤(e)中通入氮气占通入氢气和氮气总和的体积百分比为23%,其余步骤和参数与实施例22相同。
试验例2
对实施例15-21以及对比例2方法得到的含氮氢化硅薄膜进行折射率和消光系数测定,具体测定方法与试验例1中相同。
测试结果如表2所示。
表2
Figure PCTCN2018071606-appb-000003
由表2可以看出,通过采用本发明方法(氮气占氢氮混合气体比例5~20%)得到的含氧氢化硅薄膜在940nm的折射率在3.0-3.3,可获得高折射率、吸收小的薄膜。
图5为940nm下氮气占氢氮混合气体的比例对含氧氢化硅薄膜折射率和消光系数的影响。
如图5所示,氮气占氢氮混合气体的比例对含氮氢化硅薄膜折射率和消光系数有影响,随着氮气比例的增大氢化硅薄膜的折射率下降,而消光系数逐渐上升,当氮气占比超过20%时,消光系数上升明显。
对比例2与实施例18相比,通入氮气占通入氢气和氮气总和的体积百分比为23%,虽然折射率较高,但消光系数也较高,不能满足需要。
实施例22、实施例23与实施例18相比,虽然反应源功率不同,但折射率和消光系数 相差不大,实施例24与实施例18相比,反应源功率较大,而结果表明在该溅射系统下采用实施例1的溅射参数能够获得更好的效果。
实施例25与实施例18相比,增加了对基体温度的限定以及对退火工艺的限定,能够有利于提升稳定性。
实施例28
一种滤光叠层,包括多个实施例3的高折射率含氧氢化硅薄膜和多个SiO 2薄膜,多个实施例3的高折射率氢化硅薄膜和多个SiO 2薄膜交替堆叠,实施例3的高折射率氢化硅薄膜厚度为100nm,SiO 2薄膜厚度为200nm,滤光叠层厚度为5μm。
实施例29
一种滤光叠层,包括多个实施例17的高折射率含氮氢化硅薄膜和多个低折射率含氧氢化硅薄膜(实施例7),两者交替堆叠,高折射率含氮氢化硅薄膜厚度为100nm,低折射率含氧氢化硅薄膜厚度为100nm,滤光叠层厚度为3μm。
试验例3
使用实施例28的滤光叠层镀制的940nm中心波长的带通滤光片0-30°入射的实测光谱曲线,如图6所示。
使用实施例28的滤光叠层镀制的850nm中心波长的带通滤光片0-30°入射的实测光谱曲线,如图7所示。
使用实施例29的滤光叠层镀制的940nm中心波长的带通滤光片0-30°入射的实测光谱曲线,如图8所示。
使用TiO 2滤光叠层镀制的940nm中心波长的带通滤光片0-30°入射的实测光谱曲线,如图9所示。
结果表明,图6中偏移量小于14nm,最大透过率大于94%,图7中偏移量小于11nm,最大透过率大于94%。图8中偏移量小于12nm,最大透过率大于94%。
使用TiO 2、Ta 2O 5、Nb 2O 5等传统高折射率设计940nm的带通滤光片,其中心波长随角度偏移较大(约30nm),并且膜系总厚度厚(是本发明的厚度的2-3倍),意味着生产效率较低。如图9所示,相比可知,用本发明材料镀制的滤光片具有更好的光谱特性。
尽管已用具体实施例来说明和描述了本发明,然而应意识到,在不背离本发明的精神和范围的情况下可作出许多其它的更改和修改。因此,这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。
工业实用性
(1)本发明高折射率氢化硅薄膜的制备方法的溅射过程和反应过程是分开的,相对独立的,溅射过程靶材不易被反应气体污染,有效避免靶材中毒问题。该方法使生产效率得到提升,降低了成本。获得的含氧或含氮的氢化硅薄膜具有较高的折射率和更低的吸收。
(2)本发明高折射率氢化硅薄膜的制备方法得到的氢化硅薄膜,其薄膜折射率高,吸收低。
(3)本发明的滤光叠层以所述含氧或含氮的氢化硅薄膜作为高折射率材料制得,其透过率高,且具有中心波长偏移量较小,信号损失少、信噪比高等优势。
(4)本发明的滤光片,包含了上述滤光叠层,因此具有与上述滤光叠层相同的优势,使得制成的滤光片具有较高的透过率且中心波长偏移量小。

Claims (16)

  1. 一种高折射率氢化硅薄膜的制备方法,其特征在于,包括以下步骤:
    (a)通过磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
    (b)硅薄膜在含有活性氢和活性氧的环境中形成含氧的氢化硅薄膜,活性氧的数量占活性氢和活性氧总数量的4~99%,或,
    硅薄膜在含有活性氢和活性氮的环境中形成含氮的氢化硅薄膜,活性氮的数量占活性氢和活性氮总数量的5~20%。
  2. 按照权利要求1所述的高折射率氢化硅薄膜的制备方法,其特征在于,步骤(b)中活性氧的数量占活性氢和活性氧总数量的4~70%,或,活性氮的数量占活性氢和活性氮总数量的5~18%;
    优选地,步骤(b)中活性氧的数量占活性氢和活性氧总数量的5~20%,或,活性氮的数量占活性氢和活性氮总数量的5~10%。
  3. 按照权利要求1或2所述的高折射率氢化硅薄膜的制备方法,其特征在于,包括以下步骤:
    (a)在存在惰性气体的条件下通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
    (b)在存在氢气、氧气和惰性气体混合气体的条件下通过RF或ICP对混合气体活化,形成等离子体,等离子体与硅薄膜反应,形成含氧的氢化硅薄膜,其中,氧气占氢气和氧气混合气体的体积百分比为4~99%,优选4~70%,进一步优选5~20%,或,在存在氢气、氮气和惰性气体混合气体的条件下通过RF或ICP对混合气体活化,形成等离子体,等离子体与硅薄膜反应,形成含氮的氢化硅薄膜,其中,氮气占氢气和氮气混合气体的体积百分比为5~20%,优选5~18%,进一步优选5~10%。
  4. 按照权利要求3所述的高折射率氢化硅薄膜的制备方法,其特征在于,步骤(a)中Si靶溅射功率为额定功率的5%-80%,优选20%-80%,进一步优选40%-80%,进一步优选40%-70%,进一步优选50%-70%;和/或,步骤(b)中通过RF或ICP对混合气体活化的功率为额定功率的5%-80%,优选5%-50%,进一步优选15%-50%,进一步优选20%-50%。
  5. 按照权利要求3所述的高折射率氢化硅薄膜的制备方法,其特征在于,包括以下步骤:
    (a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
    (b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氧气和氩气,形成等离子体,与硅薄膜发生反应,形成含氧的氢化硅薄膜,反应源为RF或ICP等离子体激发源;
    其中,溅射源的功率为额定功率的5%-80%,反应源的功率为额定功率的5%-80%,通入的氧气占通入的氢气和氧气总和的体积百分比为4~99%。
  6. 按照权利要求3所述的高折射率氢化硅薄膜的制备方法,其特征在于,包括以下步骤:
    (a)干净的基体放在真空溅射反应镀膜机的转动机构上,镀膜面朝向靶材,转动机构在镀膜腔室内匀速旋转;镀膜腔室内真空度高于10 -3Pa时,开启溅射源并通氩气,通过MF磁控Si靶溅射,在基体上沉积Si,形成硅薄膜;
    (b)随着转动机构转动,基体被带往反应源区域,开启反应源并通氢气、氮气和氩气,形成等离子体,与硅薄膜发生反应,形成含氮的氢化硅薄膜,反应源为RF或ICP等离子体激发源;
    其中,溅射源的功率为额定功率的5%-80%,反应源的功率为额定功率的5%-80%,通入的氮气占通入氢气和氮气总和的体积百分比为5~20%。
  7. 按照权利要求5或6所述的高折射率氢化硅薄膜的制备方法,其特征在于,所述转动机构选自转盘、滚筒和转架杆中的一种。
  8. 按照权利要求5或6所述的高折射率氢化硅薄膜的制备方法,其特征在于,所述镀膜腔室设置有用于将所述镀膜腔室分割为第一腔室和第二腔室的挡板,所述溅射源位于所述第一腔室内,所述反应源位于所述第二腔室内。
  9. 按照权利要求5或6所述的高折射率氢化硅薄膜的制备方法,其特征在于,所述镀膜腔室设置有气体混合腔,氢气、氧气和氩气分别通入所述气体混合腔,混合均匀后通入所述镀膜腔室进行活化;或,
    氢气、氮气和氩气分别通入所述气体混合腔,混合均匀后通入所述镀膜腔室进行活化。
  10. 按照权利要求5或6所述的高折射率氢化硅薄膜的制备方法,其特征在于,在步骤(a)中,在开启溅射源之前,还包括加热基体至基体温度为100-300℃,接着通入氩气对镀膜腔室和基体进行轰击清洗;清洗完毕后,关闭氩气,再次将镀膜腔室内真空度抽至高于10 -3Pa;
    优选地,轰击清洗的时间为1~5min,轰击功率为额定功率的5%-80%。
  11. 按照权利要求5或6所述的高折射率氢化硅薄膜的制备方法,其特征在于,在步骤(b)结束后,还包括将所述含氧的氢化硅薄膜或所述含氮的氢化硅薄膜在退火炉内100-300℃退火60-180min。
  12. 按照权利要求9所述的高折射率氢化硅薄膜的制备方法,其特征在于,对所述含氧的氢化硅薄膜或所述含氮的氢化硅薄膜在退火炉内退火包括:
    以升温速率为1-15℃/min的速度升温至100-300℃,时间为30-60min;
    接着保持恒温在100-300℃,时间为30-120min;
    接着以降温速度为10-30℃/min的速度降温至室温。
  13. 采用权利要求1-12任一项所述的高折射率氢化硅薄膜的制备方法得到的高折射率氢化硅薄膜,其特征在于,所述高折射率氢化硅薄膜在800~1100nm波长范围内的折射率为1.46~3.7,所述高折射率氢化硅薄膜在800~1100nm波长范围内的消光系数小于0.0001。
  14. 一种滤光叠层,其特征在于,包括多个根据权利要求13所述的高折射率氢化硅薄膜和多个低折射率薄膜,多个高折射率氢化硅薄膜和多个低折射率薄膜交替堆叠,其中,所述低折射率薄膜为在800~1100nm波长范围内折射率小于所述高折射率氢化硅薄膜在800~1100nm波长范围内折射率的薄膜。
  15. 按照权利要求14所述的滤光叠层,其特征在于,所述低折射率薄膜为二氧化硅薄膜;
    优选地,所述低折射率薄膜为低折射率氢化硅薄膜,所述低折射率薄膜为在800~1100nm波长范围内折射率小于所述高折射率氢化硅薄膜在800~1100nm波长范围内折射率的薄膜;
    优选地,滤光叠层的层数为10~100层;
    优选地,滤光叠层的厚度为1~10μm。
  16. 一种滤光片,其特征在于,其包含如权利要求14或15所述的滤光叠层。
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