TW200540965A - Thin film deposition method and thin film deposition apparatus - Google Patents

Abstract

This invention relates to a thin film forming method. It comprises an optical characteristic adjusting procedures: Firstly, it repetitively transfers a substrate holder (13) between the regions for performing an intermediate thin film-forming step. Further, the region performs a film composition converting step. Furthermore, while controlling the transfer speed for the substrate holder (13) used to hold a substrate, it adjusts the film composition of the thin film to be finally formed. Eventually, it forms a thin film with an optical characteristic value in a region, where a hysteresis phenomenon takes place.

Description

200540965 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to the production of thin films on substrates, which are formed by splashing money, and are required. Base ore devices, especially in manufacturing methods, and the like. Thin films that require optical properties [Previous technology] In the past, in order to target specific mouth properties, we have been trying to use natural spectroscopic films with natural light;: ;; :::. However, it is more complicated to design an optical thin film using a substance having such properties. To obtain and have a V substance to design an optical thin film, it is necessary to find a thin film with special characteristics. That is, it is not a teacher who exists in the self-expectation. The materials for f leather and μ-money, which are anti-band reflection prevention films, must have a material with a natural refractive index in the natural world (for example, glass with a wide refractive index) to make the reflection of broken glass wide). If the emissivity is normal, it is necessary to have a wide-area "low reflection to obtain the intermediate refractive index mentioned above, and a person skilled in the art has the following techniques...: Wide Shishi low refractive material {for example, Si〇2 (refractive index: 146)}" The same refractive material {such as Ti〇 (refractive origin evaporates at the same time, depending on the ratio ^^. 35)}, respectively, from a different steam from & Hachiman to intermediate refractive index (1.46 ~ 2.40) Materials are mixed, and an evaporation source is used to obtain the intermediate refractive index technology according to its mixing ratio; a low-emission material and a high-refractive material are combined to obtain the equivalent intermediate refractive index technology. 200540965 Also, as a metal that can obtain the refractive index test, which is controlled in a semi-random manner, and has stable optical characteristics, etc., perform the technology of "generating Mn mongolian thin film". · 〇 ... · Emissivity: "Every dry base metal made of high-refractive material {such as Ding 102 (refractive index: 2.35)} is formed on the substrate to form an ultra-thin, thin metal composed of a composite metal. Silly, contact this ultra-thin film with the active species of the reactive gas of Qishang, and make the above ultra-thin film and reactive gas; sex =: convert to compound metal compound, repeat the above steps, so it is formed on the substrate and right A method of forming a thin film of a compound of a metal having a desired film thickness and optical characteristics, and a technique of / ° (for example, 'Japanese Patent Laid-Open Patent Publication No. 26 (page 2-3, figure)). Also, to separate Independent at least-inspecting plating, forming inconsistent metal or composite metal on the substrate

The ultra-thin film composed of reactants, A then contacts the formed ultra-thin film with an active species mixed with an inert gas (pre-inert nature) of reactive gas and reacts to 'convert into a compound of a compound metal' and repeat the above steps. A technique for obtaining arbitrary optical characteristics by using the inherent optical properties of a single compound of a metal (a compound film used to form a composite metal) (for example, Japanese Patent Laid-Open No. 2GG1-G116G5 (Page 2.4, Figure υ) The method of refractive index and optical characteristics of the thin film formed by the process of the reactive gas introduced into the reaction process region or the film-forming process region is also known. Ρ However, no matter whether the low-refractive material and the high-refractive material are different from each other, the source is the same, the technology of obtaining the intermediate refractive index according to its mixing ratio 'or the low-refractive material and the high-refractive material are mixed, and one evaporates. Source with d: 6 200540965

It evaporates at a time, and is based on its mixing ratio. The technique of paying the middle refractive index based on the ratio of Ⅰ, p, and A; or the combination of a refractive material and a high-refractive material A 9 from low A to serve the equivalent intermediate refractive index. Film technology, etc .; In these technologies, it is difficult to control the refractive index to a product of stable quality, which is the problem. Fukou here is to propose the following technology 'is to make each number composed of low-refractive material and high-refractive material: After the super-thin film formed by Xiao Λ, the super-thin film is brought into contact with the virtual structure, so that the ultra-thin film and the anti-reflection Reservoir,-Α, reactive species of reactive alum are converted to Α hard " metal compounds, and the above steps are repeated to form a thin film of compound metal compound with desired: thick and optical properties on the substrate / The term "also" so-called "ultra-thin film" is used as a thin film due to the ultra-thin film sub-deposition, which is used to avoid confusion with W ". Its thickness is more than that of the final" thin-film ". According to this technology ’, although the refractive index arbitrariness and mechanical properties can be obtained,

/ ... metal compound thin film, but the number of species of metal must be used as A to form Xiba ® for Geba use, although the metal compound thin metal composed of composite metal can be obtained, the emissivity can be anvil k Μ The use of early metals to form a gold alloy that has been manufactured in 4 ways, and has stable optical properties and mechanical properties, such as the optically specific compound, old amine guggan, has its difficulties, which is the problem. Therefore, in the case of using a separate gold eyebrow from the implementation: Shiriishi a wire, II is adjusted by the optical characteristics of the reactive film introduced and also sputter-plated ... to adjust the formed thin film to The optical properties of the refractive index and extinction coefficient, such as ^^, use oxygen as a reaction. However, as shown in Fig. 8 and Fig. 9, for example, 200540965 11 is used, the flow rate of oxygen and the optical characteristics of the film ( The relationship between the refractive index and the v-light coefficient) is taken as an example. When the oxygen flow rate is in an extremely high or low range _ B inch 'Although the oxygen flow rate can be adjusted by changing the oxygen flow rate (refractive index and extinction coefficient), When the oxygen flow rate is below 15 sccm (excluding 0 sccm), the relationship curve changes sharply. In order for the formed film to have the refractive index and extinction coefficient corresponding to the oxygen flow rate in the β-xuan range, a strict oxygen flow rate must be performed. Of adjustment. • As shown in Figs. 8 and 9, when the oxygen flow rate is increased and decreased, the so-called hysteresis phenomenon in which the refractive index and the extinction coefficient of the optical characteristics of the film are different is obtained. Therefore, it is difficult to control the optical characteristics of the thin film by adjusting the oxygen flow rate. The degree of difficulty is further south. 'It is intended to form a range of the refractive index of about 15 to 35 and an extinction coefficient of about 1.0 x 10-3 to 12. For a film in the range of χ 10.3, strict adjustment of the oxygen flow rate is required. • Therefore, by adjusting the oxygen flow rate to form a thin film having a refractive index and an extinction coefficient in the aforementioned range, the reproducibility is poor depending on the range of the oxygen flow rate. Membrane is very difficult. Therefore, a technique for forming a thin film having a refractive index and an extinction coefficient having optical characteristics in this range has been expected. Therefore, the present invention was made in view of the above-mentioned problems, and an object thereof is to provide a method for manufacturing a thin film and a sputtering apparatus which use only a single metal. The film is manufactured with high reproducibility, and its optical characteristic value is located in the area where the 200540965 hysteresis phenomenon (the path of the optical characteristic value varies according to the flow rate of the reactive gas). [Summary of the Invention] The thin film forming method of the present invention is characterized by having the following steps: An intermediate thin film forming step is performed by sputtering with a target composed of a single type or a plurality of types of metal, and forming a metal or an incomplete metal on a substrate An intermediate thin film composed of oxide; a step of changing the composition of the film, contacting the formed intermediate thin film with an active species of a reactive gas mixed with an inert gas (chemically inert) to make the intermediate thin film reactive with the reactive gas A compound that reacts to be converted into a metal; and an optical characteristic adjusting step of controlling the transfer speed of the substrate holder for holding the substrate to cause the substrate holder to perform the intermediate film formation step and perform the The film composition conversion step is repeatedly transferred, and the intermediate thin film formation step and the film composition conversion step are repeatedly performed, thereby adjusting the film composition of the finally formed film to form a thin film. The optical characteristics of the film have a hysteresis phenomenon ( Where the flow of reactive gas increases and decreases, The optical path changes to different characteristic values of gas flow rate size) of the region. In this way, if the substrate holder is formed to be movable between the film formation process area (for implementing the intermediate film formation step) and the reaction process area (for implementing the film composition conversion step), and the moving speed of the substrate holder can be adjusted In this way, the sputtering time in the film formation process area and the reaction time between the intermediate rhenium film and the reactive species of the reactive gas in the reaction process area can be reduced. Therefore, the composition of the finally formed thin film can be adjusted, and the film can be easily formed with high reproducibility. Its optical characteristic value is located in the area where hysteresis can occur, and 200540965 is the control of the optical characteristic value of the film. There are difficult areas. At this time, in the optical characteristic adjusting step, it is preferable that the substrate holder (which holds the substrate in a cylindrical shape or a hollow polygonal column shape on the outer peripheral surface) is driven to rotate, and the substrate holding is controlled by With the rotation speed to form the desired film, the optical properties of chirp are located in the region where the hysteresis can be generated.

Thereby, the substrate held in the substrate holder can be smoothly and repeatedly transferred between the film formation process region and the reaction process region, and the transfer speed can be stably controlled by controlling the rotation speed of the substrate holder. In addition, Tian Yu can simultaneously sputter money on a large number of substrates held on the outer peripheral surface of the substrate holder to form a thin film, and can mass-produce thin films. The area where the hysteresis occurs is the optical characteristic value area of the thin film formed when the reactive gas Ic introduced in the sputtering process is 15 sccm or less (excluding Osccm). In the region, because the optical characteristics of the reactive gas flow rate are large: and the hysteresis phenomenon is generated, it is very difficult to control the optical characteristics of the formed thin film by the reactive gas flow rate. … "In this area, the optical film of the formed thin film is not controlled by the adjustment of the flow rate of the reactive gas, but the adjustment of the special rotation speed. A reproducible film formation with the desired optical characteristics & thin film formation The shovel holder is specially equipped with a substrate board that is arranged in the vacuum; Γ to hold the substrate; a film-forming process area, which belongs to the target formed by the name of soap-type or plural types Those who form an intermediate film on the substrate again; reaction 10 200540965 process area, which is arranged in the vacuum tank, has an active species generating mechanism for generating reactive species of reactive gas, and makes the intermediate film and Reactivity = active species react with each other to form a thin film; the separation mechanism is used to separate the film formation process region and the reaction process region from each other; the substrate holder driving mechanism is used to drive the substrate holder to face the substrate The substrate is transferred between the position of the film-forming process region and the position facing the reaction process region; the substrate holder transfer speed control mechanism is a substrate holder within the range where a thin film can be formed. The optical mechanism of the film is located in a region where hysteresis can occur (in the case where the flow rate of the reactive gas is increased and decreased, the path of the change in the optical characteristic value of the reactive gas flow is not used) In this way, by having a substrate holder driving mechanism (for driving the substrate holder to move the substrate between a position facing the film formation process region and a position facing the reaction process region) and a substrate holder transfer Speed control mechanism (used to control the transfer speed of the substrate holder). Only setting the transfer speed of the substrate holder can easily form a thin moon with the desired optical characteristics and its reproducibility is higher than adjusting the reactive gas flow rate. The optical characteristics of the formed thin film. The area where the hysteresis phenomenon occurs is the optical characteristic value of the thin film formed when the reactive gas flow rate is 15 SCCm or less (excluding Osccm). Here »A τ 'Since the reaction The change of optical characteristics of the nature of the gas flow rate is based on the fact that the X's and Z's's have a hysteresis phenomenon. Gas flow I te | It is very difficult to make the optical characteristics of the thin film formed. 200540965 In this area, 'not through the adjustment of the reactive gas flow rate, and • f by the rotation of the substrate The speed can be adjusted to control the optical characteristics of the formed thin film, and the thin film with the desired optical characteristics can be formed with high reproducibility. Other advantages of this month can be made clearer by the following summary. Embodiment] The present invention relates to a thin film forming method and a base plating device for forming a thin film on a substrate by sputtering. Hereinafter, embodiments of the present invention will be described with reference to the drawings and described below. The members and the arrangement of the members are not intended to limit the present inventor, and various changes are possible within the scope of the gist of the present invention. 2 In this embodiment, in order to obtain the target optical characteristic value and film thickness, the intermediate film must be repeatedly implemented Film formation and reaction to form a thin film. The range of the optical characteristic value of the target film 'means that a hysteresis phenomenon occurs (single or multiple types of metals are used _ when the flow rate of the reactive gas introduced during film formation increases and decreases, depending on the reaction ! · The optical characteristic value of the area where the size of the optical characteristic value is not used in the lice body machine. FIG. 1 is an explanatory diagram showing a sputtering apparatus according to this embodiment. Fig. 2 is a cross-sectional explanatory view of the branch of the spoon line A B-C. In the present embodiment, magnetron sputtering is used (a spatter of splashing money is used, but it is not limited to this, and other well-known methods such as 2-pole money without magnetron discharge can also be used). Sputtering device for sputtering ... The main components of the sputtering device of this embodiment include: vacuum 200540965

Only said 11 is a substrate holder 13 for holding a substrate (film to be formed, not shown) in a vacuum tank ij, and a servo motor 17 for driving the substrate holder i3 as a substrate holder driving mechanism for controlling The servo motor port is a control device 90 for the substrate holder with a transfer speed control mechanism, and is used to implement the film formation process zone 20 of the intermediate film formation step, so that the intermediate film formed in the film formation process zone is reactive with an inert gas. The reactive species 60 in contact with the active species of the gas and performing the film composition conversion step are used to form the partition wall 12, 16 as the partition mechanism of the reaction private area 60, and the magnetron sputtering electrode 21a as the sputtering electrode. 21b, AC power source U, an active species generating device 6i for generating active species as an active species generating mechanism. —Eight—In the present specification, the so-called intermediate thin film is made of a metal or a metal element-free full oxide and is formed in a film forming process region. The vacuum tank 11 is generally used in a known sputtering device. A hollow body in the shape of a cube. The shape of the vacuum tank 11 may be sigma-column. An exhaust pipe is connected to the bottom surface of the vacuum tank 11. Here, as shown in FIG. 2, the piping is connected as shown in FIG. 2, so that the vacuum tank 11 can be lined up ^ ”I 1 5. The vacuum pump 1 can be used by this 5 and a controller (not shown) to adjust the degree of vacuum in the vacuum tank u. The substrate holder 13 is arranged at the approximate center of the vacuum tank 11. The substrate is secured in a cylindrical shape, free from ^ 1 3 The shape of the plurality of earth-reverse substrate holders 13 held on the outer peripheral surface may not be a cylindrical shape but a hollow multi-column shape, and it may also be a substantially conical shape of Zhonggong. The substrate holder 1 3 is connected to a vacuum; ^ I Ί / ~ 9 forms a state of electrical insulation, that is, potential floating. The substrate holder 13 is arranged in the vacuum chamber so that the central axis Z in the same direction between the circles is directed toward the vacuum chamber 11 1 13 200540965 downward. The substrate holder 3 is maintained in a vacuum state inside the vacuum tank 11 'by a servo motor 17 provided on the upper part of the vacuum tank 11 and driven to rotate around the center axis Z. The servo motor 17 is a well-known servo motor, and is controlled by a tethering device 90 as a control mechanism. The substrate holder 13 is rotated by the driving of the servo motor 7 and its rotation speed can be arbitrarily controlled within the range of 10 rpm to 150 rpm. • A substrate holding mechanism (not shown) is provided on the outer peripheral surface of the substrate holder 13 to hold the substrate in the soil plate holder. 1 3 A recessed portion (not shown) and a recessed portion that can accommodate the substrate are placed in the substrate holding mechanism. Form a row in the up and down direction. In this embodiment, a flat substrate is used, that is, a thin-film forming surface of the substrate (hereinafter referred to as a "film-forming surface") and an opposite surface of the film-forming surface (hereinafter referred to as a substrate back surface) are parallel to each other; a substrate is formed. The base of the holding mechanism is designed so that when holding the substrate, the surface opposite to the back surface of the substrate of the recess is oriented in a direction perpendicular to the central axis Z of the substrate holder 13. Therefore, the film formation surface of the substrate is oriented in a direction perpendicular to the central axis Z of the substrate holder 13. The film forming process region 20 and the reaction process region 60 are formed by partition walls 12, 16 fixed in the vacuum tank 11. The film-forming process region 20 is formed in a state surrounded by the partition wall U, and the reaction process region 60 is formed in a state surrounded by the partition wall 16. In this embodiment, the reaction process area 60 is fixed to the vacuum tank 11 ′ and the partition wall 16 is set to the formation position of the self-film forming process area 20 based on CS: 14 200540965 plate holder 1 3 + 疋 The axis of rotation is about 90 degrees around the center, and the position on the substrate is rotated by the motor Π. The substrate on the holder 丨 3 can be held at the "// 13," and held on the substrate plate. The position facing the film formation process area 20 and the reaction process area 60 can be shifted between the position of the door spoon and the face. By this, the The target 29a 9〇κ of the film formation process area 20 is relatively moved to a target (2%, 291) to be described later. Also, the surfaces of the partition walls 12 and 16 in the present embodiment are in the shape of an open cylinder + # _… ^ 1 pair of pairs ... 枰 ... 枰 ": Qian Gangzhi. Partition wall 12, the side wall attached to the true "say" and the side wall of the substrate holder 丨 the side wall of the groove π is held toward the substrate ... At this time, the area The state of one door and two directions of the next walls 12 and 16 is fixed, sideways, $ ea open on one side, and it is fixed to the inside by abutting to the vacuum tank holder 13 of the vacuum tank 11. Partition walls 12 and 16 are respectively provided with water cooling accessories (not shown) to cool the partition walls 12 and 16. In the film forming process area 20, through the allocation of $ ,, ☆ 妣 妣 &. S company ... There are 4 working systems 2 5 as the rolling body introduction mechanism. This flow control cry (Qing Qing) Xi Xia Zagu ^ Hour 25 is connected to the year-old mine south pressure gas storage argon gas (inert gas month beans) Hm 27 and the reactive south exhaust gas container 79 storing anti-li gas It . This anti-shore remedy ^ "", ά ά 夂 夂 夂 夂 夂, can be self-reactive high-pressure gas capacity 2: operation: 1 li under the control of the controller 25 into the film formation process area: oxygen: for The reactive gas may be, for example, oxygen, nitrogen, or gas. In the film formation process region 2G ′, a magnetron sputtering electrode 2 is disposed on the wall surface of the vacuum chamber U so as to face the outer peripheral surface of the substrate holder 13. & Chuan. This magnetron ㈣ electrode 21a, 2lb is fixed to a vacuum tank u forming a ground potential through an insulating member not shown. Magnetron ^ electrode 仏, 15 200540965 21b, is connected to an AC power source through a transformer 24 23, to apply an alternating electric field. The square magnetron electrode 21a, 21b holds the targets 29a, 29b. The shape of 29a, 29b is a flat plate, and the targets 29a, 2b and the outer peripheral surface of the substrate holder The opposing surface is perpendicular to the center axis Z of the substrate holder 13. Also, although the illustration is omitted, it may be disposed between the targets 29a, 29b and the substrate holder Η in the film forming process area 20. Removable pre-sputter for shielding or opening between the dry 29a, 29b and the substrate holder 13. Shield. This pre-sputtering shield is used to shield between the targets 29a, 29b and the substrate holder 13 before the sputtering is stabilized, and then make the targets 29a, 29b and the substrate holder until the sputtering is stable. Open between 1 and 3, so that the sputtered atoms can be deposited on the substrate after the coin plating reaches a stable state. An opening is formed on the wall surface of the vacuum tank 11 in the reaction process area 60, and the opening is connected to the opening. An active species generating device 6 1 as an active species generating mechanism. The active species generating device 6 1 (also referred to as a radical source) is provided with a reactive gas plasma generating device composed of a quartz tube for generating a reactive gas plasma. The chamber 63 ′ is wound around a coil-shaped electrode 65 of a reactive gas plasma generation chamber 63, a matching box 67, a high-frequency power source 69 connected to the coil-shaped electrode 65 through a matching box 67, a flow controller 77, and A reactive high-pressure gas container 79 connected through a flow controller 7 7. A reactive gas plasma generating chamber 63 in the active species generating device 61 1 generates a plasma generated by discharge, using plasma ions, electrons, and free Freedom , Atoms, molecules, etc. as a constituent element.

(I 16 200540965 The reactive species of reactive gas in the plasma generated in the reactive gas plasma generating chamber 63 can participate in the reaction within 60 of the reaction process zone. The so-called reactive species of reactive gas refer to ions , Free radicals, etc. Also, the so-called free radicals are radicals, which are atoms or molecules with more than one unpaired electron. X, the so-called excited state (like ..., refers to a stable base state ( Lowest energy state).

Reactive gas such as oxygen from the reactive pressure gas container 79 through the flow controller 77 is supplied to the reactive gas plasma generating chamber 63, and high-frequency power from the high-frequency power source 69 is passed through the matching box 67 and is applied to The coil-shaped electrode 65 generates the plasma of the reactive gas in the reactive gas plasma generating chamber 63 in this way. As shown in Figs. 1 and 2, an external magnet 7 丨 is disposed outside the reactive gas plasma generating chamber 63, and an internal magnet 73 is disposed in the reaction process area 60. The outer magnet 71 and the inner magnet 73 generate a high-density plasma by forming a magnetic field of 20 to 300 Gauss in the 7-plasma generating section to improve the efficiency of generating active species. In this embodiment, both the outer magnet 71 and the inner magnet 73 are provided. However, either the outer magnet 71 or the inner magnet 73 may be configured. For the following, the above-mentioned sputtering device of this embodiment is used.

The description of the field entry of a silicon dioxide (SiO2) derivative thin film. Don't take σ as an example. In the book of this situation, as the target, it is explained by using silicon or. However, it can be made from ★ dagger horse example as a target user. It is not limited to the single _ Lishuo's gold 17 200540965 genera. That is, even when plural kinds of metals are used as the leather, the optical characteristics of the film can be controlled by controlling the rotation speed of the substrate holder within a range where hysteresis occurs. (Formation steps of silicon oxide film)

First, the targets 29a and 29b are placed in a sputtering apparatus i. The substrate is held on the substrate holder 13 by a substrate holding mechanism. The target 29a, 2%, I do not keep the magnetron sputtering electrode 21a, 21be as the magnetron electromagnetism: The material of 21a, 21b is silicon (Si). The range of the optical characteristic value of the target film is in the case where the hysteresis phenomenon occurs (sputtering with a target made of a single type or multiple types of metal, when the flow rate of the reactive gas is increased and decreased, depending on The area where the flow rate of the reactive gas does not change the optical characteristic value). The so-called hysteresis phenomenon refers to a phenomenon in which the b value of the same a is not the same according to the change path of A when the other quantity B changes with the change of the quantity A. In this specification, it means that the process is performed on a single type or a plurality of types of metal. The reaction, the amount of gas emitted increases and decreases the path, and the refractive index and A phenomenon in which values such as the extinction coefficient change. Next, the vacuum tank 11M is decompressed to a predetermined pressure, and the servo motor 17 is operated to start rotation of the substrate holder 13. The rotation speed of the substrate holder 3 is selected from a range of a rotation speed of 100 rpm to 100 rpm (and preferably a range of 10 rpm to 60 rpm). The rotation speed of the film is controlled by the setting of 18 200540965 device 90. Thereafter, after the pressure in the vacuum sample _ ^ is stabilized, the pressure in the film forming process region 20 is adjusted ^ U X 10- 丨 ~ 1.3Pa. Next, use machine money ^ ^ ^ < argon as an inert gas and oxygen as a reactive rolling body, from the supply of guangzhou π,, ώ θ, 又 'a pressure gas container 27, reactive high pressure gas capacity Gong 790 was introduced into the film-forming process zone 20 with flow control and ^ ^ °° 5 to adjust the flow rate, and adjusted to an ambient atmosphere where sputtering can be performed in the film-forming #, sleep table & zone 20. At this time, the flow rate of the argon gas introduced into the film formation #,, &% & 20 was about 300 sccm. And adjust the flow rate of oxygen introduced into the film-forming process zone 20 to the household as described later: the required value ° sccm as the unit of the flow rate is expressed in (TC, ⑽25Pa day-the flow rate per minute, equal to cm3 / min Then, by the households, the power supply 23 passes through the transformer 24 and applies an AC voltage of 1 to 100 kHz to the magnetron sputtering lb to apply two alternating electric fields to the targets 29a and ^. At this point, the coarse 29a at a certain time point becomes the cathode (the target 29b of negative 0 inch inch must become the anode (positive electrode). At the next time point, the direction of the AC changes. At this time, |,, and leather 29b become the cathode (negative electrode) And target 29a ^ positive electrode 2. In this way,-pairs of targets 29a, 29b alternately become anodic "poles" to form a plasma, and the target on the cathode is sputtered. At the beginning, the Before the stable operation, the wire holder = 13 is held by a pre-keyed key shield, and the plate 29 is not opened between the dry 29a, 29b and the substrate holder 13 until the plating removal can be performed. After the plutonium reaches a stable state, the plutonium atoms are deposited on the substrate plutonium. During the spattering process, a non-conductive material is combined on the anode. Or low conductivity 19 200540965: Incomplete oxides such as oxidized stones are attached. However, when this anode is converted into a cathode by an alternating electric field, these incomplete oxides of silicon will be: The surface of Ibar is in the original clean state. Furthermore, the-pairs of targets 29a and 29b alternately become the anode and the cathode, which can always obtain a stable anode potential state and prevent the plasma potential (usually approximately the same as the anode potential). ), Stable silicon film formation on the substrate film formation surface =

In this manner, by performing sputtering in the film formation process region 20, an intermediate thin film made of silicon or a silicon incomplete oxide is formed on the film formation surface of the substrate. The silicon incomplete oxide is an incomplete reactant in the present invention, and is an incomplete silicon oxide lacking oxygen in the constituent elements of silicon oxide Si02. The composition of the material constituting the intermediate film is determined by the adjustment of the flow rate of oxygen introduced into the film-forming process zone 20, and the film thickness of the intermediate film is determined by the adjustment of the rotation speed of the substrate holder 13. That is, the relationship between the flow rate of oxygen introduced into the film-forming process area 20 and the stoichiometric coefficient χ of the incomplete oxide SiQx (x < 2) constituting the intermediate film is the flow rate of oxygen following the introduction The larger the value, the larger the stoichiometric coefficient X is. In addition, if the rotation speed of the substrate holder 13 is accelerated, the time spent in the film formation process area will be shortened, so the number of particles deposited on the substrate will be reduced, and the thickness of the intermediate thin film will be thinner. In this embodiment, the flow rate of the introduced oxygen gas is adjusted to a desired value so that silicon is formed on the film formation surface of the substrate or a silicon incomplete oxide having a desired stoichiometric coefficient χ is formed. The thickness of the film is 20 200540965 square f, and the rotation speed of the substrate holder 13 is 5 for 5 weeks, so that the sputtering zone is formed in the red zone 20 of the film-forming clothing. During sputtering, the substrate holder is rotated at a predetermined rotation speed, and an intermediate film made of silicon or an incomplete oxide of silicon is formed on the film formation surface of the substrate. Moreover, although not shown, the electrodes 21a, 21b and the substrate can also be held by magnetron sputtering! A correction plate and a shielding plate are provided between 3 to form an intermediate film having a film thickness distribution corresponding to the shape of the shielding plate.

In the film formation process area 20, an intermediate thin film composed of silicon or silicon incomplete oxygen is formed on the film formation surface of the substrate. After the intermediate thin film forming step is performed, the substrate is faced to the surface by driving the substrate holding 4 13 The position of the film processing area 20 is transferred to a position facing the reaction processing area 60. In the present embodiment, in the reaction process region 6G, the incomplete oxide of the stone thin film constituting the intermediate thin film is subjected to an oxidation reaction to be converted into an oxide state (oxidation state 102) to perform a film composition conversion step. In the reaction process zone 60, the self-reactive high-pressure gas container 79

Introduction of oxygen for reactive gases. Apply high-frequency power of ~ 5GMHz to the coil-shaped electrode M, and use an active species generator to produce the product.

Health plasma. In addition, the pressure in the reaction process zone 60 was maintained at 7.0 × 2 to 1.OPa. An active species of the reactive gas is present in the plasma in the reactive gas plasma generating chamber 63, and the active species of the reactive gas is introduced into the reaction process area 60. As a fool, the board was held in place, and the substrate of the intermediate film composed of Qiaotian Noble or Shi Xi's incomplete oxide was transferred to the reaction-oriented system ^ 6. Position, in the reaction process zone 6 ", so as to form the intermediate film :: 21 200540965 to make silicon or silicon incomplete and convert it to incomplete oxide oxides to carry out the oxidation reaction step. That is, the full oxide is oxidized by the active species of oxon and alum. The rotation speed of silicon (SiO2) 0 U can be determined. At this time, the composition of the thin film between substrate holders is adjusted.

The force-speed substrate holder has a rotation speed of 13. The film thickness of the intermediate film formed in the film-forming process zone will become thinner, which makes the reaction in the reaction process zone 60 easier. Therefore, the stone and stone in the reaction process zone The proportion of incomplete oxides (to be converted into silicon oxide (Si〇2) will become higher. That is, in the reaction process area 60, the silicon and stone that are converted to silicon oxide (Si〇2) are incomplete. The amount of oxide is changed according to the rotation speed of the substrate holder $ ，, and the composition of the formed thin film is also changed according to the rotation speed production of the substrate holder 13. ^ = mouth and the rotation speed of the substrate holder 13 is adjusted The composition of the silicon and silicon incomplete oxide (Si0j, silicon oxide (SiO2)) that constitute the finally formed thin film can be adjusted, and the optical characteristics of the finally formed thin film can be determined according to the composition of the thin film. The composition of the film can be determined by adjusting the rotation speed of the substrate holder 13 to form a film having the desired optical characteristics. Figure 3 shows the relationship between the rotation speed of the substrate holder 13 and the optical characteristics of the formed film. Evaluation of the thin optical properties The parameters are the selection of the refractive index and the extinction coefficient, the horizontal axis represents the rotation speed (rpm) of the substrate holder, and the vertical axis represents the refractive index and the extinction coefficient. 22 200540965 ^ As shown in Figure 3, according to the thin film formation method of this embodiment, The refractive index of the formed film can be increased between k ⑨2 · 〇2 ～ 1.475 with the increase of the substrate holding speed of 13㈣, and the extinction coefficient can be controlled between 16 乂 10 · 2 ~ 5 · 0 X 10 · 5 In this embodiment, the rotation speed (rpm) of the substrate ## 13 is determined so as to form a thin film having a desired refractive index and an extinction system according to FIG. 3 according to FIG. 3. The optical characteristics of the thin film are used. The data measured by the spectroscopic ellipsometry were evaluated. Table 1 shows the rotation speed of the substrate holder in this embodiment and the substrate transit time in the film formation process zone and the reaction process zone. [Table 1] Rotation speed (rpm) Film formation speed (nm / second) Sputtering time (second) Film thickness before reaction (nm) Reaction time (second) 150 0.2 5.63E-2 5.39E-2 140 0.2 6.04E-2 1.21E-2 5.77E-2 130 0.2 6.50E-2 1.30E-2 6.22E-2 120 0.2 7.04E-2 —ldl ^: 2 6.74E-2 110 0.2 7.68E · 2 1.54E-2 7 35F-2 100 0.2 8.45E-2 __Κ69Ε-2 8.08E-2 90 0.2 9.39E-2 1.88E · 9 8 98E-2 80 0.2 1.06E -1 \ j · yo jo 1.01E-1 70 0.2 1.21E-1 2.41E > 2 1 15F-1 60 0.2 1.41E-1 2.82E ^ 2 1 * 1 · w L · ^ X 1 3SF-1 50 0.2 1.69E-1 1.62E-1 40 0.2 2.11E-1 — _ 4.23E-2 2 02E-1 30 0.2 2.82E-1 5.63E-2 2 69E-1 20 0.2 4.23E-1 ^ 145 ^ 2 4.04E -1 10 0.2 8.45E-1-* —---- Lj ^ 69E-l 8.08E · 1 So, by adjusting the rotation speed of the substrate material, it can be controlled at 23 ^ 200540965 = in the film processing area. The time and the reaction time in the reaction process zone can control the composition of the finally formed thin film. One. Also in this reaction process zone 6〇 中 脍 组成 aa # ^ ^ ^ ^ in the film composition conversion step, the phase film thickness is thicker than the film thickness of the intermediate film to form the most transformation =, forming the intermediate film The incompletely cut oxide is called ㈣) Cut (SlC > 2), which swells the membrane of the towel, making the film thickness of the thinnest mosquito boat thicker than that of the intermediate film. The most ... specific expansion rate depends on the introduction to the film forming gong. h The flow rate of oxygen in the film-forming process zone 20, that is, in the middle of the film-forming process zone 20 ^ y & P, Zuo Zhuangsha, Jie < T between the formation steps, the slave makes Toad formation in the film-forming process area is reduced by 1 L and the value of the stoichiometric coefficient x of the silicon incomplete emulsion is decreased. The increase rate of the film is increased. S change, the step of forming the intermediate film JI ^ · ^ m does not catch on introducing the deposition, into the m decision Cloth intermediate film composed of silicon: the stoichiometric composition of the I ... [chi] (Ruoshi constituted by silicon-based ...), And decided to increase the rate relative to the 1 # M. ] The final film thickness of the Tao film is limited in this embodiment. 'As described above, the rotation speed of the base side is controlled while the substrate holder on which the substrate is mounted is rotated. ^ Enter the intermediate film formation steps and film. The composition conversion step is repeated in the formation of silicon on the substrate in the film-forming process area 20, and the formation of silicon (II) (S10x (x < 2)) in the reaction process area, and in the reaction process area 6G;-conversion of oxides to oxidation Shi Xi (SiO2) can form a thin film with the desired optical properties of 7 ^ X oxidation. The required film thickness and the required rs 24 200540965 or higher 'are for the description of forming a thin film by silicon sputtering, and the same can be used to form a thin film by niobium sputtering. Fig. 4 shows the relationship between the substrate rotation speed of the niobium oxide derivative film and the optical characteristics of the thin film. … As the evaluation parameters of the optical characteristics of the formed thin film, the refractive index and the Shaw optical system are selected. The horizontal axis represents the rotation speed (㈣) of the substrate holder, and the vertical axis represents the refractive index and extinction coefficient. As shown in Figure 4, according to the thin film forming method of this embodiment,

The refractive index of the resulting thin film can be increased with the rotation speed of the substrate holder 13 and I is made between 3.50 and 2.35. The extinction coefficient can be controlled between & 5 X ΪΟ-2 and 5.0 X 10.5. In this embodiment, the speed of the substrate holder 13 (rpm) is determined in accordance with FIG. 4 so that a thin film having a desired ratio and an extinction coefficient is formed. In fact, the operating conditions of the field where the silicon is formed by sputtering. Listed below are the cases where thin films are formed according to this embodiment (1) Sputtering conditions of silicon Input power · 7.0k \ V Substrate temperature: Pressure in the room temperature film-forming process zone: 1.3Pa AC voltage frequency: 40Khz Complete compound film-forming speed: 04nm / s (2) Niobium sputtering conditions Input power: 4.5kW Substrate temperature: room temperature 25 200540965 Pressure in the film-forming process zone: l.3pa AC voltage applied Frequency ·························································· 35. ·· 2.0kW pressure: 6.5 X l〇-ipa

In the above embodiment, the materials used for the riding are Shi Xi and Rui, but it is not limited to this, and the materials of the targets 29a and 29b can be variously modified. ⑷ For example, you can use Ming⑷), titanium (Ti), erbium, tin ㈣, iron (⑺, group (Ta), pound (Te), iron (Fe), town (Mg) 'to (Hf), nickel (Metals such as dysprosium, indium-tin (In-Sn), and the like. Compounds of these metals can also be used, such as: Al203, Ti02, Zr02, Ta205, Hf02, etc. In the case of a target, it can be made into Al203, Ti02, Zr02, TaA, Si02, Hf02, MgF2 by contact with the reactive species of the reactive gas in the reaction process area 60. Optical films such as insulating films, conductive films such as IT0, magnetic films such as FeA3, superhard films such as iN, CrN, TiC, etc. (b) In the above embodiment, as shown in FIG. It has a configuration in which the same reactive co-pressure gas valley ^ § 7 9 introduces a reactive gas into the film formation process zone 20 and the reaction process zone 60, but it is not limited to this, and the film formation can also be performed. The process region 20 and the reaction process region 60 are connected to different high-pressure gas containers, and different gases having the same elements are introduced. In the above embodiment, the oxygen guide 26 200540 is used as a reactive gas. 965 enters the film formation process zone 20 and the reaction process zone 60, but in addition, t can be: oxidizing gases such as ozone, nitrous oxide (N2O), etc. Gases such as carbonic gas such as oxane, fluorine, carbon tetrafluoride, fluorinated gas, etc. In addition, the introduction of nitrogen into the film formation process area M ^: the flow rate of the introduced gas' inert gas argon can be _, Nitrogen can be 9 to 60 sccm. ⑷ In the above embodiment, 'as a reactive gas plasma, as shown in Figure 1, Figure 2', used outside the reactive gas plasma generation chamber or PX electrode 2 The coupling-type plasma source " 隹 can also be used as described later. An inductively-coupled plasma source (hereinafter ⑴) and a capacitor-type plasma source ( The following ⑺), inductive light-capacitive coupling type plasma source (the following (3)), etc. (1) The electric ㈣ shown in Figure 5 (A): a disc-shaped quartz glass, etc. The structure of the pore body electropolymerization generating chamber 63 "the spiral side of the spiral electrode (mosquito incense) 91 on the atmospheric side, : ΙΟΟΚΗζ ~ 5GMHz of local-frequency power to generate the electric induction # generating source. Figure 5 (B) is a plan view of the spiral electrode 91. Electric water (2) The electric source shown in Figure 6: A flat plate ... 93 is arranged inside the gas electro-polymerization generating chamber 63. For this flat plate electric tank, high-frequency power of ~ Hz is generated to generate a source of f ^. Valley coupling type plasma (3) The electricity shown in Fig. 7 Plasma source: The coil-shaped electrode 95 or spiral electrode is arranged inside the reactive gas electropolymerization, and the high-frequency electric power of pulse HZ ~ Xiao HZ is applied to generate 27 * 200540965 plasma and capacitive coupling plasma exist) Plasma generation source. In addition, by adjusting the shape of the coil, etc., a spiral wave plasma source can be made, and the generation efficiency of the active species in the plasma can be improved. In the above embodiment, a so-called rotary sei type base ore device is used, but it is not limited to this. That is, even if the substrate holder is not driven to rotate, any sputtering device capable of repeatedly transferring the substrate holder between the film formation process region and the reaction process region and controlling the transfer speed is acceptable. For example, it may be a sputtering apparatus that repeatedly moves the substrate holder in parallel. The processing of the step “Process of the film and the process of changing the composition of the film” is the same as the method of manufacturing a thin film using sputtering fi as described in the above embodiment, and is adjusted by adjusting the transfer speed of the substrate holder. The ore sputtering time and reaction time can determine the optical characteristics of the formed thin film. ^ As described above, in the method for forming a thin film of the present invention and a device for forming the thin film, the rotation speed of a substrate holder for transferring a substrate between a film formation process region and a reaction process region can be adjusted. Film thickness and light of the thin film [Simplified description of the drawing] Fig. 1 shows the description of the t-spattering device of the present invention. Fig. 1 shows the cross-sectional explanatory diagram along the line ABC of the present invention. Figure existence. Figure 3 shows the optical characteristics of the thin film on the rotation speed of the substrate holder. Figure 4 shows the optical characteristics of the T film on the rotation speed of the substrate holder on 28 200540965. 5 (A) and 5 (B) are explanatory diagrams showing a configuration example of a plasma source. Fig. 6 is an explanatory diagram showing a configuration example of a plasma source. FIG. 7 is an explanatory diagram showing a configuration example of a plasma source. FIG. 8 shows the oxygen flow rate dependence of the refractive index of the film. Fig. 9 shows the oxygen flow rate dependence of the extinction coefficient of the film. [Description of main component symbols]

(IZ Central Axis 1 Sputtering device 11 Vacuum tank 12, 16 zone partition wall 13 Substrate holder 15 Vacuum pump 17 Servo motor 20 Film forming process area 21a, 21b Magnetron deactivation electrode 23 AC power source 24 Transformer 25 ^ 77 Flow controller 27 Sputtered high-pressure gas container 29a, 29b Target 60 Reaction process area 61 Active species generating device 63 Reactive gas plasma production 29 200540965 65 Coil-shaped electrode 67 Matching box 69 Local frequency power source 71 External magnet 73 Internal magnet 79 Reactive high-pressure gas Container 90 Control device 91 Spiral electrode 93 Flat electrode 95 Coil electrode

(1 30

Claims (1)

200540965 10. Scope of patent application: 1. A method for forming a thin film, which is characterized by having the following steps: A step of forming an intermediate thin film, sputtering a target composed of a single type or a plurality of types of 4 metals, and forming a target on the substrate. Intermediate film composed of metal or metal = complete oxide; & a film composition conversion step, contacting the formed intermediate film with an active species of a reactive gas mixed with an inert gas (chemically inert) to make the intermediate film The thin film reacts with an active species of the reactive gas to be converted into a metal compound; and < " Optical characteristic adjustment step 'to control the substrate holding speed of the substrate holder to control the transfer speed of the substrate holder It is provided to repeatedly transfer between the region where the intermediate thin film formation step is performed and the film composition conversion step, to repeatedly perform the intermediate thin film formation step and the film composition conversion step, and to adjust the film composition of the finally formed film to form a thin film. The two optical characteristic values are located after the generation of hysteresis. Areas where the flow path of the reactive gas increases and decreases when the flow rate of the reactive milk varies according to the size of the low-response milk flow. ▲ 2. If you apply for a patent _ 1 item A method for forming a thin film, wherein, in the optical characteristic adjustment step, driving a β substrate holder (which holds the substrate in a cylindrical shape or a hollow multi-self-thinking angle column on the outer peripheral surface) to rotate and control the The rotation speed of the substrate holder is used to form the desired thin film M, and its optical characteristic value is located in the area where the hysteresis phenomenon can occur. 3. For example, the method for forming a thin film of the scope of item 1 of the patent application, where the hysteresis phenomenon occurs in the area 'Reactive gas introduced when money is sputtered 31 200540965 The optical characteristic value range of the thin film formed when the flow rate is 15 sccm or less (excluding 0 sccm). 4. A thin film forming device, comprising: substrate holding Tools, which are arranged in a vacuum tank to hold the substrate; the film-forming process area is arranged in the vacuum tank, and can be controlled by a single type or a plurality of types A target made of metal is sputtered on the substrate to form an intermediate film; a reaction process area is arranged in the vacuum tank, and has an active species generating mechanism for generating active species of a reactive gas, and The intermediate film reacts with the active species of the reactive gas to form a thin film; a separation mechanism is used to separate the film forming process area and the reaction process area from each other; A person who moves the substrate between the position of the film processing area and the position facing the reaction processing area; and a substrate holder transfer speed control mechanism for controlling the substrate holder driving mechanism within a range where a thin film can be formed, the The optical characteristic value of the film is located in a region where hysteresis can occur (in the case where the flow rate of the reactive gas is increased and decreased, the path of the optical characteristic value of the reactive gas flow rate is not used). Health 4 = A thin film forming device with a patent scope, where the range of eight jade stones is the optical characteristic value range of the thin film formed when the reactive gas flow rate is 15 sccm or less (not δ 0 sccm). (S 32 200540965 11.