TW583324B - Method and equipment for growing a thin film in a low temperature - Google Patents

Abstract

A method for growing a thin film in a low temperature and a thin film growing equipment are disclosed. First, raw solid powders or solid powder particles formed by in-situ drying the dispersed liquid suspension are dispersed to form an aerosol by mixing the solid powder particles and carrier gas. Then, the aerosol is guided into a powder processing chamber. Second, the aerosol is processed by glow-discharge or microwave to generate the low temperature plasma, or by shined by laser or light onto the solid powder particles surfaces. Finally, the solid powder particles are accelerating to hit a substrate to form a thin film. The equipment includes a material, an aerosol forming device, a surface processing chamber and a substrate.

Description

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[Application field to which the invention belongs] A invention relates to a method and a device for growing a thin film, and particularly to "a kind of functional thin film containing highly volatile elements, such as ferroelectric materials, Method and equipment for low-temperature growth of thin films made of conductive materials or composite materials. [Previous technology] The growth of thin film elements such as ferroelectric films, after more than ten years of development, has now developed a variety of Growth technologies, including physical vapor phase bonding films (RF sputter, Magnetron sputter, Ion-beam sputter, ECR plasma, Excimer laser ablation, etc.), chemical vapor phase coatings (MOCVD, LUui (i sourece CVD), wet-type Growth method (so; l-gel, MOD), MBE, etc. However, at present, these thin film growth technologies still need to be grown under the environment of Nanwen, about 5,000-700 degrees Celsius above can be good The nature of strong dielectrics. However, 'high temperature growth will lead to problems such as difficulty in controlling the composition of the film, large residual stress, and interdiffusion. ~ In addition, Akedo et al. Tried to use aerosol (aer〇s 〇1) Growth method to produce ferroelectric thin films (J. Akedo et al., SenS (^ s &

Actuators, A69 (1998), 106-112, Appl. Phys · Let ·, 77 [11] 1710-12 (2000)), however, this method still needs to be heated at a temperature of 50 ° C or higher Processing, can get good ferroelectric properties. In addition, NP Rao et al. Instantly synthesized nano-scale particles (n a n 0 s t r u c t u r e d) in a high-temperature plasma (about 10,000 degrees Celsius).

583324 _Case No. 90128396__Year Month and Day Amendment _ V. Description of the Invention (2) The method of spraying a gas stream on a substrate to form a thin film is called a hypersonic plasma particle deposition method (Hypersonic Plasma)

Particles Deposition, HPPD) (J. Aerosol Sci., 29 [5/6] 707-20 (1998)). However, in such a high-temperature plasma, it is not easy to control the composition of a multi-component film ', especially a film having a highly volatile element component (such as a ferroelectric thin film). Another solution is the method of Schmitt, which uses nozzles 0 to react with gas through resistance wire heating or to form a stream of solid particles by reacting gas or liquid V into the reaction, and sprays it on the substrate at a high speed. 1> Thin films, however, it is still not easy to form multi-component thin films such as ferroelectric thin films. [Summary of the Invention] In view of the above-mentioned conventional technologies, a method for low-temperature growth of a thin film and a temperature-control heat treatment, which is easy to control the composition, and a thin film. The question "The purpose of the present invention is to provide a preparation". It can be made into a special method and equipment that does not require subsequent high residual stress and small interdiffusion. It can be used to form a thin film on the surface of the raw material with low removal. It is easy to control the composition according to the disclosed growth method of the present invention, and includes the following liquid suspension, the aerosol produced by the instant gas. The purpose is to warm the plasma, thunder and activate the present invention. Technology, step-by-step method: Introduce the dry material into the powder to provide a shot or light, and then supply the thin, high-quality solid powder processing room of the present invention; to perform the method of colliding the raw material with the equipment and the film. Provide a thin solid powder particle, and then, grow the treatment, hit the base to get a low or dispersed film.

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583324 _Case No. 90128396_ 年月 日 __ V. Description of the invention (4) Poor. Use this pressure difference to accelerate the aerosol. The surface treatment can be formed inside or outside the nozzle or simultaneously inside and outside the nozzle. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, several preferred embodiments are exemplified below, which are described in detail with the accompanying drawings as follows: [Embodiment] Please refer to the first Figure, a flowchart of the low-temperature growth method of the film of the present invention, the thin-film growth method of the present invention includes the following three main steps: forming the raw material into aerogel containing powder particles (step 110), and surface-forming the powder particles Processing (step 1 2 0) and growing the film (step 1 3 0). First, the present invention can be applied to a variety of metal or ceramic materials, and is particularly suitable for materials containing highly volatile elements (such as Pb, Bi, Tl, Li, Na, K, etc.), including: 1. Strong dielectric materials: Pb (Zr, Ti) 03, PbTi03, LiNb03,

LiTa03, (Na, K) Nb03, NaNb03, SrBi2Ta2 09, etc .; 2. Dielectric materials: Pb (Mn, Nb) 03, LiAlSi2 06, etc .; 3. Superconducting materials: B i Sr2 CaCu2 Ox, B i Sr2 Ca2 Cu3 Ox, T 1 B a2 C a2 C u3 Ox, T 1 B a2 C a C u2 Ox, etc. 4 · Battery materials: Lix Co2, LixMnY Oz, Lix Ni i Co02, Li iMn2 04, etc. 5. Composite materials: Composite materials containing any one or more of the above and other metals, ceramics or polymers. Secondly, after selecting the materials, the technology provided by the present invention can be applied according to the manufacturing requirements. In step 110, the present invention firstly solid-state powder or dispersed suspension liquid two different types of materials are first dried in-si tu

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Case No. 90128396 V. Description of the invention (5) = Cheng Gan f mixes the carrier gas to form a gel containing raw materials. Among them, the size of the plutonium particles is about less than sub-micrometer. Materials: In this state: the state particles become the initial material for forming the thin film of the present invention. Prepared in advance, 3 = the original solid powder or dispersion: two: powder or dispersed suspension liquid passed through the composition; solid: solid: the surface of the particles is often contaminated, such as the surface adsorbs organic matter: The next step is to perform low temperature = treatment on the powder particles in the aerosol (step 12). This process can remove the low temperature of the solid particles: the low in step 1 2 0,襞 Or use an energy beam such as Leica again / 'The present invention uses a kind of low powder particles to be irradiated first' to remove solid particles after aerosol, basin surface = plus: activation, after the low temperature Two methods of surface treatment (low temperature, meter surface or line. Among them, 'generating low temperature electricity—equipment; = single use or simultaneous discharge) or microwave irradiation— = light discharge (gl〇w- can produce Low-temperature plasma gas: "Song zone The gas can be carried by the gas. Or it can carry gas, but it can be other than "raw milk" and other "emulsions, nitrogen, etc. and gas. The mixture of rolling and non-inert gas: to carry another gas-as desired U-body, another aspect, then, the step of carrying the raw material of the film i2〇), page 9 583324

The aerosol component of the dry nail can be directly formed into a thin film (step 丨 3㈧. After the aerosol subjected to low-temperature surface treatment, as long as the solid particles are accelerated, the solid particles can be directly hit on the substrate to grow into a uniform and dense component According to the invention, the above-mentioned operation method of the present invention is provided. The present invention further provides a low-temperature growth device for the thin film. Please refer to the first specific embodiment of FIG. 2. This long and long device includes: aerosol forming device 22 〇, nozzle 23, vacuum cavity 250 and microwave plasma excitation device 31, low temperature plasma 26 °, substrate 2 70, heating stage 2 80, and microwave plasma excitation device 3 丨 〇; The vacuum-like evils of the cavity 250 are obtained by vacuum pump (yacuum p㈣), and the support frame 2 90 is responsible for supporting the substrate. 〃 ^ The working principle of the microwave plasma is to use external high-frequency electromagnetic waves (4 waves) electrons Acceleration can be obtained when the electromagnetic wave is generated, and the accelerated electrons impinge on the gas to dissociate the gas to form a plasma. The first specific embodiment of the present invention uses a solid powder of Pb (Zr, Ti) 03 as a raw material. 'Put the solid powder into the aerosol forming device 2 2 0, carry the gas (enter from the inlet 210), pass the aerosol forming device 220 to form the aerosol, and spray it into the vacuum cavity 25 through the nozzle 230.携带. The carrier gas system is mixed with chlorine gas (Ar) and oxygen gas (〇2) in a ratio of three to one, and the total gas flow rate is 0.5 to 1.0 litres per minute. Aerosol forming device 22 to the nozzle The pressure of 2 3 0 is maintained at about 160 Torr (Qorr), and the pressure in the vacuum chamber 2 5 0 is evacuated to 丨 · 5 to 2.5 Torr. The diameter of the mouthpiece is one millimeter (mm) ◦ Nozzle 2 The principle of accelerating the aerosol is to use the pressure difference between the inside and outside of the nozzle 230, that is, if the outlet of the nozzle 230 is inside the moon space 250, so it has a pressure difference between the inside and outside, so that the gas can be released. 583324 Fix

Case No. 90128396 V. Explanation of the invention (7) The solid particles 240 carried by the glue accelerate toward the vacuum cavity 25 〇 240 and rush towards the substrate 27 within the vacuum cavity 2 50 and are maintained by the addition of 埶 / 280 below it. The temperature of the substrate 270 is between room temperature and 200 degrees Celsius. Day: Mouth 1 The microwave plasma excitation device 31 generates a microwave and aerogel reaction, that is, 2V: carries Λ gas, generates a low-temperature plasma 26 ° ′ and removes solid particles: 240. In this way, the body particles 24 are rushed toward the substrate 2 after the surface treatment. That is, a dense film with good characteristics can be formed on the substrate surface. According to the device and technology provided by the present invention, the solid β can be seen from the scanning electron microscope photos provided in Figure 4 and Figure 5; please refer to Figure 4 for the non-electropolymerization treatment. Figure 5 shows the titanic acid structure; the body work surface microstructure. Figure 5 shows the microstructure of the first embodiment of the present invention. Comparing Fig. 4 and Fig. 5, it can be clearly seen that the denseness of the thin film that will be treated by Mei Lei is much higher than that of the lead zirconate film that has not been treated with plasma. In addition, measure again *-text: show the properties of the thin film produced in the specific example, and compare the results: :: Table 1 Dielectric Constant (K) at 100kHz Dielectric Loss (tan (5) at 100kHz Conventional Aerogel Film Growth method 160 0036 ~~~~ Substrate temperature (room temperature) of the first embodiment 390 0.029 ^ Substrate temperature (200 ° C) of the first embodiment 700 0036 ~ From this, it can be known that the film properties can be improved by the present invention. Dense film 583324

Go * Or, you can do another way of powder surface treatment to energy

The biological and control device 330 produces laser or light, and the laser or light ^ irradiates the aerosol, and the surface of the solid particles 24o carried by the aerosol will not be treated 'under the conditions of the species'. Generates low temperature plasma. That is, the carrier gas need not be specifically selected for the generation of the low-temperature plasma 26o. In addition, the energy beam generating and controlling device 33 can also be a glow discharge, microwave generating device 'and can be designed as a laser or light generating device at the same time, that is,' generating two types of energy beams; Glue to generate low-temperature plasma, a kind of energy beam can assist surface treatment. Finally, the surface-treated solid particles 240 directly hit the substrate 27 at a high speed to form a thin film. Below the base plate 270, a heating stage 28 is set. The base plate 270 can be heated to an appropriate temperature through the adding stage 280 to obtain a suitable composition; The lightning, water, dust, water, and water treatment processes can be performed separately within the nozzle 230 or outside the nozzle 230, or inside or outside the nozzle 230 Simultaneously. That is, when the decontamination process is performed separately in the nozzle 230, the low-temperature plasma 260 can be formed in the nozzle 230, that is, the aerosol is located in the nozzle 230, that is, an energy beam, a glow discharge, or a microwave, etc. When the decontamination process is performed outside the nozzle 230, a low-temperature plasma 260 may be formed outside the nozzle 230. In other words, when the aerosol is located outside the nozzle 230, the aerosol is irradiated with energy beams, glows, red winds, or microwaves to generate plasma, which is the situation in Fig. 2; When the decontamination process is performed simultaneously inside the nozzle 2 3 0 and outside the nozzle 2 3 0, when the field and / or the king of the wood are on for 1 minute, the low-temperature plasma 2 60 can be used on the same day inside and outside the nozzle 2 3 0 The formation of 'that is, the aerosol is located inside and outside of the spray 0' are all energy beams, glow discharges or squares ... __ 臓 《臓! 1 面 rigid shed 丨 丨 1 丨 丨 丨 ------ 583324 _ Case No. 90128396 _ year month day __ V. Description of the invention (9) Glue makes the gas in the aerosol to form a low-temperature plasma 260. At the same time as the above-mentioned generating of low-temperature plasma, a laser or light generating device can also be used in combination with aerosol for surface treatment and activation of the powder. The gas that can form a low-temperature plasma, that is, the carrier gas that forms an aerosol, can be an inert gas, such as helium or neon, or a non-inert gas such as oxygen or nitrogen. In addition, it can be A mixture of inert gas and non-inert gas. If the raw material is in the form of a dispersed suspension liquid, it must be added to a process, that is, a process of drying first. In this prior drying process, traditional heat sources or special heat sources (such as infrared, ultraviolet, resistance wire, or microwave, etc.) can be used for instant drying to form aerosols. The specific implementation device is shown in FIG. 3, which is the second specific embodiment of the low-temperature growth device of the film of the present invention. Comparing Figure 2 and Figure 3, it can be found that the only difference is that a heat source 32 0 is installed between the carrying gas inlet 210 and the aerosol forming device 22 0, which can dry the liquid suspension to form the desired dry powder. . The remaining devices have the same content and will not be described again. According to the device and technology provided by the present invention, the specific effects of the present invention can be seen from Figs. 4 and 5. Please refer to Fig. 4. Lead zirconate titanate (Pb (Zr Ti) 03) The surface microstructure of the thin film. Figure 4 shows the surface microstructure of the first specific embodiment of the present invention. Comparing Fig. 4 with Fig. 5, it is obvious that the film density of Fig. 4 is much higher than that of Fig. 5. [Effect of the invention] The low-temperature growth method and equipment using the film of the present invention can achieve

Page 13 583324 _Case No. 90128396_Year Month Date__ V. Description of the invention (10) Films grown at low temperature, such as ferroelectric thin films, which are easy to control, have low residual stress, and have no problems with interdiffusion. Although the preferred embodiment of the present invention is disclosed as described above, it is not intended to limit the present invention. Any person skilled in the related art can make some changes and retouching without departing from the spirit and scope of the present invention. The patent protection scope of the invention shall be determined by the scope of the patent application scope attached to this specification. 583324 Case No. 90128396 Revised diagram Brief description Briefly, Figure 1 is a flowchart of the low-temperature growth method of the film of the present invention; Figure 2 is the first specific embodiment of the low-temperature growth device of the film of the present invention; Figure 3 This is the second specific embodiment of the low-temperature growth equipment of the film of the present invention; FIG. 4 is the surface microstructure of the lead titanate titanate film without plasma treatment; and FIG. 5 is the first specific embodiment of the present invention Surface microstructure. [Illustration of Symbols]

210 Carry gas inlet 220 Aerosol forming device 230 Nozzle 240 Solid particles 250 Vacuum cavity 260 Low temperature plasma 270 Substrate 280 Heating table 290 Support stand 300 Vacuum pump 310 Microwave plasma excitation device 320 Heat source 330 Energy beam generation and control device Page 15

Claims (1)

583324 Case No. 90128396 Patent Application Method for low-temperature growth of thin films, including the following steps: solid powder containing a raw material or a dispersed liquid suspension is instantaneously dried to form a solid powder particle, and carried by a The aerosol generated by the gas is introduced into a powder processing chamber; the solid powder particles are subjected to a powder surface treatment process in the powder processing chamber in a low temperature surface treatment manner; and the powder particles after the treatment are processed The thin film is formed by accelerating and impinging on the substrate to perform surface densification. 2. 3. 6. How about patent application? The method for low-temperature growth of the thin film described in the first item of the scope, wherein the particle size of the #solid evil powder particles is about sub-micrometer or less. For example, the method of low temperature growth of the 溥 film described in the first blind place in the patent application scope # 屌 封 粗 Z Γ, the thin film material of the volatile element 'ceramic tile' body, especially suitable for the third The low Λ growth method containing high volatile element exaggerated amidine, dielectric materials, superconducting materials, and samarium membrane materials include: ferroelectric materials, such as the 4th place of the patent application scope 1, battery materials and Composite materials. The low-temperature growth of the volatile thin film on the surface of this strong medium is 〇3 'LlNb〇3 strong [^ material, selected from PbUr *, T1) 03, 312%. Grade ^^ '. (Heart, 〖) Heart 03, ^ Heart 03 and the method as in the scope of patent application No. 4, the low-temperature growth of the high-volatile film of this age UNb〇3, LlTa () 3, (Nm is selected from the group consisting of Pb (zr, T〇 () 3, PbT103, C a, K) Nb〇3, NaNb〇3 and SrBi2Ta209 Page 16 583324 _ Case No. 90128396_ Year Month Amendment _ 5, the scope of the patent application into a group. 7. The method for low-temperature growth of a highly volatile film as described in item 4 of the scope of patent applications, wherein the superconducting material is selected from BiSr2CaCu2Ox, B i Sr2 Ca2 Cu3 OX, T 1 Ba2 Ca2 Cu3 0X, and T 1 Ba2 CaCu2 A group of 0X. 8. The method for low-temperature growth of a thin film as described in item 1 of the scope of patent applications, wherein the low-temperature surface treatment method uses a glow discharge (g 100w-discharge) or a microwave to irradiate the aerosol to generate the carrier gas A low-temperature plasma is used for powder surface treatment. 9. The method for low-temperature growth of a thin film according to item 1 of the scope of patent application, wherein the low-temperature surface treatment method uses laser or light to irradiate the aerosol to perform powder surface treatment. 10. The method for low-temperature growth of a thin film as described in item 1 of the scope of patent applications, wherein the low-temperature surface treatment method uses a glow discharge (g 100w-discharge) or microwave to irradiate the aerosol to generate a low-temperature electricity Slurry, and simultaneously irradiate the aerosol with laser or light to perform powder surface treatment. 1 1. A device for low-temperature growth of a thin film, comprising: a raw material, which is first processed to form a solid powder particle as a raw material for forming a thin film; an aerogel forming device for forming the solid powder particle with a The carrier gas forms an aerosol; an acceleration device for accelerating the aerosol containing the solid powder particles; Page 17 583324 y 3 a I γρ _ Case No. 90128396 ^ ------ VI. Patent application scope-Energy beam generating device for irradiating the aerogel to activate the surface treatment of the solid powder particles And a substrate for receiving the impact of the accelerated and surface-treated solid powder particles, and forming the film on the surface of the substrate. 1 2. The method for low-temperature growth of a thin film as described in the scope of patent application No. 丨 i, wherein the particle size of the solid powder particles formed is about sub-micron. 1 3 · The device for low-temperature growth of thin films as described in item 1 of the patent application scope, wherein the raw materials can be metal or ceramic materials, especially suitable for materials containing high volatile elements. 1 4. The device for low-temperature growth of a thin film as described in item 3 of the patent application scope, wherein the material containing high volatile elements includes: ferroelectric materials, dielectric materials, clock battery materials, superconducting materials, and Composite material. 15 · The device for low-temperature growth of a thin film according to item 14 of the scope of patent application, wherein the ferroelectric material is selected from the group consisting of Pb (Zr, Ti) 〇3, pbTi03, LiNb〇3, LiTa03, (Na, K) Group consisting of Nb〇3, NaNb03 and S r B i 2 T 〇9 16 · The device for low-temperature growth of highly volatile films as described in item 14 of the scope of patent applications, wherein the dielectric material is selected from the group consisting of Pb (Zr, Ti) 03, PbTi〇3, LiNb03, LiTa03, (Na , K) A group consisting of Nb03, NaNb03 and SrBi2Ta2 09. 1 7. The device for low-temperature growth of high-volatile films as described in item 14 of the scope of patent applications, wherein the superconducting material is selected from BiSr2cacU20x, 8131 " 20 and (: 1130) (, D13320 ~ (： 113 (\ 和 丁 16 & 2〇 & (: 112 (^ Page 18 583324 Case No. 90128396 _η said Amendment 6. Scope of Patent Application. 18. The 11th longest device in the scope of the patent application, wherein the high-volatility thin-film beam generating device described in this energy item is a glow (g 1 0w-discharge) or microwave generating device, which The powder is made so that the carrier gas is generated. 1 9. The long device as described in item 11 of the scope of patent application, wherein the energy beam generating device is used to perform powder surface 2 0. The long device as described in item 11 of the scope of patent application, wherein the energy beam produces (glow-discharge) or microwave generation device for powder table 2 1. As in the patent application scope No. 1 1 preparation, wherein the acceleration device is formed, the aerosol system sends an external pressure difference from the nozzle to accelerate the gas gum. The low-temperature photo-discharge device that emits the high-volatile film at the surface of the aerosol is a laser or photo-processing device. The highly volatile thin film plant includes a plant and a side treatment. The low-temperature forming nozzle and a vacuum chamber of the thin film described in the above item pass through the vacuum chamber and are generated by the low-temperature forming glow discharge laser or light-length device. Page 19