JP4920202B2 - Surface processing method of semiconductor processing carrier member and article thereof - Google Patents

Description

Detailed Description of the Invention

The present invention provides a surface with improved wear resistance, corrosion resistance, and contamination resistance of a polishing semiconductor processing carrier member for ultra-smoothing the surface of a silicon semiconductor substrate or a compound semiconductor substrate such as gallium phosphide, gallium arsenide, and gallium nitride. The present invention relates to a processing method and articles thereof.

High-precision devices such as silicon substrates are used for high-speed and large-capacity digital information processing represented by personal computers, mobile phones, liquid crystal digital televisions, digital cameras, car navigation devices, and broadband information terminals. The material substrate tends to become thinner and thinner, and there has been a demand for a higher-precision ultra-flat surface than ever before.

As a method for polishing an ultrathin substrate, a lapping process or a polishing process is often employed. These are a lapping process in which a rough cut workpiece is set on a processing carrier provided with a predetermined circular hole, and then rotated and polished while quantitatively supplying a polishing liquid called slurry, and diamond fine particles are cast, Hard polishing process that pushes and rotates and polishes into a platen embedded in a relatively soft metal such as copper or tin, and also a polishing liquid (chemically active liquid) containing fine abrasive grains in a soft material such as cloth or urethane sponge There is a soft polishing processing method in which a mirror polishing is performed while rotating while supplying a fixed amount.

For polishing processing of these semiconductor substrates , it is necessary to improve the processing accuracy of various polishing apparatuses to the utmost, such as a cast housing that suppresses apparatus vibration as much as possible and has excellent vibration attenuation by the drive transmission unit, In addition, the processing accuracy, wear resistance, corrosion resistance, and contamination resistance of carrier jigs (hereinafter referred to as semiconductor processing carrier members) for fixing and rotating the substrate are increasingly required. .

Various semiconductor substrates such as stainless steel, titanium alloys, and glass epoxy resin plates are used for current semiconductor processing carrier members. During the polishing of silicon single crystal substrates , metal elution from the substrate, the substrate Damage to the carrier member, such as damage due to its own friction and wear, wear damage to the rotating gear, and metal corrosion, has a significant impact on the polishing process of ultra-thin wafers. For this reason, the present situation is that the semiconductor processing carrier member is replaced every several hundred hours and used for high quality.

Conventionally, a method of forming a diamond-like carbon film (hereinafter referred to as a DLC film) has been proposed in order to impart slipperiness to the metal material surface or the ceramic material surface. A method of forming a carbon film by a plasma CVD method using raw materials such as methane gas and acetylene gas on the surface of a member that slides with a machine part or a contact member has already been put into practical use, such as a video tape capstan roller, a small bearing, Applied to hot water and water switching valves, etc. , it exhibits excellent performance.

Reference is made to patent documents described in the following publications.
[Patent Document 1] JP 2000-96233 A discloses a plasma CVD method in which plasma generation method, applied voltage, gas composition, etc. are devised to develop a plasma CVD apparatus capable of low temperature processing as much as possible. A method of forming a diamond-like carbon film (hereinafter also referred to as a DLC film) on the surface of a plastic molded product has been proposed, and further, it has been proposed to be used for an O-ring for cameras, a wiper rubber for automobiles, and the like. However, these plasma CVD methods are methods in which the introduced gas is turned into plasma at a high frequency, and the activated carbon element is chemically reacted and deposited on the surface of the component. Therefore, the chemical reaction between the member surface and the DLC film layer is performed. Bonding strength is weak and adhesion may be poor.

  In particular, in order to process a heat-sensitive material such as a plastic material or rubber, it is necessary to generate a soft plasma by modulating a high frequency in order to reduce (weaken) the plasma density. In order to attract carbon ions in the plasma, it is common to apply a bias voltage of several tens of volts to several hundreds of volts. However, with such a voltage, the carbon element is attached to the surface layer portion of the substrate. Therefore, it is not possible to implant ions into the base material (several tens of nm or more). Therefore, in the plasma CVD method, in order to improve the adhesion to the base material, silicon as a base treatment layer, silicon oxide, silicon nitride, silicon carbide, titanium tetrachloride, pentaethoxytitanium, tetraisoproxytitanium, etc. are used. It is necessary to improve the adhesion to the substrate by introducing an intermediate layer of a compound of silicon or titanium and carbon.

  Also, in the PVD method (physical vapor deposition method) that forms a film by sputtering a carbon solid target, a DLC film is formed by heating the substrate temperature of metal or ceramic at 300 to 500 ° C. in order to improve adhesion. In addition, it was necessary to form a film by depositing silicon or chromium material, which is compatible with carbon, as a base treatment. Further, in order to attract carbon ions in plasma, it is common to apply a DC or AC bias voltage of several tens of volts to several hundreds of volts. This voltage is used as film forming energy, It is not possible to greatly improve the adhesion.

Furthermore, it is necessary to provide a device with a special reaction mechanism in order to uniformly apply the base, and a rotation mechanism is indispensable in order to ensure the uniformity of the film thickness. It could only deal with products with a certain shape. In particular, the semiconductor processing carrier member to be processed in this proposal consists of a high-precision disk having a large area ranging from 500 to 800 mm in diameter and 0.5 to 0.8 mm in thickness, and a DLC film is uniformly formed on this surface with an accuracy of 0.1 μm. There is a need to.

  In the above plasma CVD method, if the area is large, the plate material is distorted and processing accuracy cannot be obtained. In the PVD method, even if a DLC film is formed by providing a rotation mechanism, the film thickness cannot be made uniform and 1 μm. The above thickness variation occurred. Furthermore, the film forming process has become complicated in both cases, and the processing cost has increased.

With the above-described technology, it is difficult to uniformly form a DLC film on a semiconductor processing carrier member , and a process capable of forming a uniform DLC film with high accuracy and low cost without adding a complicated rotation mechanism has been desired.

In the present invention, a surface layer of a semiconductor processing carrier member composed of a high-precision disk having a large area ranging from 500 to 800 mm in diameter and a thickness of 0.5 to 0.8 mm is modified by using a plasma-based ion implantation technique (plasma based ion implantation). To form a functional DLC film. Provided is a semiconductor processing carrier member coated with a novel DLC film forming process and a high-quality DLC film, which cannot be achieved by the conventional physical film forming process (PVD) or chemical film forming process (CVD). .

A conventional diamond-like carbon film , that is, a DLC film, has high hardness and excellent wear resistance, electrical insulation, hydrophilicity, etc., but depending on the film forming method and the raw material used, the built-in hydrogen-containing flaws vary in hardness. A carbon film was obtained. In particular, the plasma CVD method, the sputtering method, the ion plating method and the like have high hardness and excellent wear resistance, but have a problem of poor adhesion to the substrate. The present invention improves the wear resistance, corrosion resistance, and contamination resistance by applying the plasma-based ion implantation / film formation method to the surface of semiconductor processing carrier members that are composites of various metal materials, ceramic materials, plastic molding materials, etc. This is provided as a surface modification technique.

In the present invention, a semiconductor processing carrier member is installed in a plasma surface treatment apparatus, a hydrocarbon-based gas is introduced into the plasma surface treatment apparatus, and the gas pressure is maintained at 0.1 to 10 Pa. A high frequency power is supplied to the member to generate discharge plasma, and a negative high voltage pulse (hereinafter also referred to as a negative voltage pulse) having a pulse voltage of 1 to 50 kV and a frequency of 100 to 5000 cycles is applied to the semiconductor processing carrier member. Further, carbon ions are implanted into the surface of the semiconductor processing carrier member, and a diamond-like carbon layer is formed on the surface . A negative voltage pulse of several kV to several tens of kV is applied to the semiconductor processing carrier member, and ions containing carbon are implanted into the surface of the semiconductor processing carrier member to form a carbon gradient layer, and the pulse voltage is controlled. However, by forming a DLC film containing carbon and hydrogen, the above-mentioned problems are solved and the object is achieved.

Semiconductor processing carrier members are not single materials, many are composite members composed of metal disc parts such as stainless steel and titanium alloy and resin gear parts such as polyimide resin, polyamideimide resin, polyetheretherketone resin, nylon resin , Alternatively, it is composed of a composite member in which disk members such as glass fiber reinforced epoxy resin and carbon fiber reinforced epoxy resin are combined. For this reason, it is necessary to form a DLC film under conditions that allow a metal or plastic film to be formed.

Vacuum chamber, the vacuum exhaust system in particular, the gas supply and control system, a high frequency power source, the negative high-voltage pulse power supply (hereinafter, referred to as the high-voltage negative pulse power supply), consists of a set frame, the high-voltage supply system cooling system The surface modification of the semiconductor processing carrier member is performed using the surface treatment apparatus . Power can be supplied to the metal member simply by connecting an electrode lead wire. However, in order to apply a voltage to an insulator such as ceramics, rubber, plastic, etc. , an electrode is placed on the back of the member or inside the member. It is necessary to supply high-frequency power to the electrode to generate gas plasma. When a negative high voltage pulse voltage is applied to the metal member and plastics member that are the injection target, electrons in the plasma are discharged, and an ion sheath is formed along the shape of the injection target. Most of the applied negative pulse voltage is applied to the ion sheath, and positive ions in the plasma are attracted and accelerated and enter along the shape of the injection target. Therefore, high energy ions are implanted into the surface of the implanted object, and a gradient layer containing the implanted ions is formed.

In the present invention, carbon ions can be implanted into insulators such as metals and plastics. In the case of applying a conventional DC bias voltage, when positive ions are implanted into the insulator, the battery is charged up and dielectric breakdown may occur. In the method of applying a high- frequency voltage and a high-voltage negative pulse voltage according to the present invention , when the pulse voltage is not applied, the plasma approaches the substrate surface, the charge charged on the substrate is neutralized, and the charge-up is eliminated. Is done. Further, by optimizing the pulse frequency and application time for each shape, it is possible to prevent dielectric breakdown and to prevent film non-uniformity and film formation speed from being lowered due to charge-up.

  It is as follows.

In the surface treatment method according to the present invention, pulsed high-frequency power (hereinafter also referred to as a high-frequency pulse) oscillating at a constant cycle is supplied to a workpiece to excite discharge plasma, and a negative voltage immediately after the high-frequency pulse. In this method, a pulse is applied to the object to be processed, and ion implantation or a DLC film is formed on the surface. Therefore, the physical properties of the film formed by the surface treatment method depend on the frequency of the high-frequency power source, the repetition frequency of the high-frequency pulse, the pulse oscillation time, etc., and the pulse voltage, pulse width of the high-voltage negative pulse power source, Depends on delay time from high frequency pulse. Furthermore, it is also influenced by the gas flow rate, gas pressure, etc. of the plasma generation raw material. A semiconductor processing carrier member having improved wear resistance, corrosion resistance, and contamination resistance by controlling these factors and implanting ions onto the surface of the semiconductor processing carrier member, which is the object to be processed, and coating the surface with a DLC film. Can be provided.

The hydrocarbon gas that is the raw material gas is a gas mainly composed of at least one selected from hydrocarbon compounds composed of methane, acetylene, benzene, toluene, cyclohexanone, chlorobenzene, and the like . A gas is introduced into the vacuum chamber, a high-frequency voltage is applied to make the source gas into plasma, thereby generating carbon atoms or molecular ions, and a negative voltage pulse is applied to accelerate the material gas. Ion implantation.

Since the discharge gas with different ratios of carbon atoms and hydrogen atoms is excited by the hydrocarbon gas , the gas species and the mixing ratio thereof are determined by the required ratio of hydrogen atoms contained in the generated DLC film . Is preferred. In methane, acetylene, benzene, and toluene gases, it is known that the degree of carbon ion implantation and the state of film formation of the DLC film vary greatly depending on whether aliphatic or aromatic, and carbon difluoride as required. By adding carbon tetrafluoride, carbon hexafluoride, sulfur hexafluoride, tetrafluorocarbon 10 and the like, a DLC film having functions such as lubricity and water repellency can be formed.

The high frequency power source for generating discharge plasma desirably has a frequency of 0.2 MHz to 2.45 GHz, an output of 10 W to 20 kW, and a pulse width of the high frequency pulse of 1 μs to 200 μs. A suitable frequency of the high frequency power source is 1 MHz to 50 MHz. The preferred pulse width of the high-frequency pulse is 30 μs to 100 μs.

According to the present invention, the physical properties of the generated DLC film also depend on the applied high frequency pulse. In a conventional mass separation type ion implantation apparatus , it is possible to inject only carbon ions by using a commercially available hydrocarbon gas such as methane or acetylene , exciting a discharge plasma by a high frequency electric field . However, in the surface treatment method according to the present invention, a negative high voltage pulse is applied to the object to be processed and accelerated directly from the plasma surface for ion implantation, so that molecular ions combined with carbon are also implanted simultaneously as impurities. The inventors of the present application have found that the following high-frequency pulse application conditions are suitable as a result of various investigations of favorable plasma conditions that can sufficiently inject carbon ions even in the presence of these extra ions.

It is necessary to optimize the application conditions of the high frequency pulse, that is, the repetition frequency, the pulse width, and the output power . When the repetition frequency is 100 Hz or less, the number of ion implantations within a certain time is reduced, and the ion implantation efficiency is lowered. On the other hand, when the frequency is 5000 Hz or higher, it is necessary to improve the performance of the high- frequency power source , and the cost of the apparatus increases. The pulse width is related to the density of the excited discharge plasma. If the pulse width is 10 μs or less, a sufficient plasma density cannot be obtained, and if it is 100 μs or more, the plasma density is saturated. Note that the high-frequency pulse can supply not only pulse oscillation but also high-frequency power that continuously oscillates.

The negative voltage pulse is preferably -1.0 to 30 kV from the viewpoints of adhesion of the film to the substrate, wear resistance, and corrosion resistance. If it is −1.0 kV or less, the ion implantation depth into the substrate is shallow, and an inclined structure between the substrate and the DLC film cannot be obtained, resulting in low adhesion . In addition, when a high voltage of −30 kV or higher is applied, the inclined structure between the base material and the DLC film advances, but the high-voltage negative pulse power source increases in size and the device cost increases. As a result, problems such as the occurrence of abnormal discharge and temperature rise due to ion irradiation occur, and the occurrence of distortion and damage of the plastic molded product becomes remarkable.

Although the ion implantation time to the surface of various base materials is not limited, it is preferably 30 to 120 minutes. More preferably, it is a short-time treatment from the viewpoint of productivity, but in the plastic molding part of the semiconductor processing carrier member, the surface layer becomes brittle due to carbon atom implantation, and the adhesion may be lowered. Must be selected.

In the conventional mass separation type ion implantation apparatus, the available ion beam current is less than mA, and it takes several hours to implant ions of 1E17 ions / cm 2. On the other hand , in the surface treatment method according to the present invention, since ions can be directly taken out from the plasma surface, a beam current of several A to several tens of A can be obtained, and a carbon ion implantation process can be performed in a short time. In addition, since the ion implantation is performed not by the DC voltage but by the pulse voltage , damage to the insulator due to the charge-up is very small.

In the carbon ion implantation method of the present invention, since the ion implantation is performed with an energy sufficient to break through the surface oxide layer, a carbon gradient structure can be easily formed . In particular, by carbon ions implanted at a high energy for the stoichiometric solid solution carbon hard non-ferrous metals, it is possible to form a DLC film while increasing the surface hardness. It is also possible to form a film while changing the DLC film formation energy and controlling the elastic modulus of the DLC film. Accordingly, the residual stress in the DLC film is low and adhesion is easily obtained. For this reason, a high-hardness DLC film having a thickness of 2.0 to 10 μm can be easily obtained in a semiconductor processing carrier member that requires wear resistance .

In addition, when a silicon substrate is polished using a highly corrosive silicon polishing solution, it is necessary to perform DLC film formation that emphasizes corrosion resistance. In a sputtering film forming method in which a conventional graphite target is used as a raw material, carbon particles called droplets are present in the DLC film, and a lot of minute pinholes are generated, resulting in a significant loss of corrosion resistance. In the carbon ion implantation + DLC film forming method of the present invention, an arbitrary amount of carbon can be implanted to form a carbon gradient structure. The DLC film formed on the surface of the carbon ion implantation has a non- hydrogen content controlled. since, as a crystalline carbon deposits can be extremely dense DLC film forming no droplets pinholes.

In this process, it is possible to form a film while controlling the elastic modulus of the DLC film by changing the pulse voltage at the time of film formation of the DLC. Therefore, the residual stress in the carbon film is low and the adhesion can be easily obtained. For this reason, it is possible to easily obtain a carbon film having a thickness of 2.0 to 10 μm, and for a semiconductor processing carrier member comprising a high-precision disk having a large area ranging from 500 to 800 mm in diameter and a thickness of 0.5 to 0.8 mm. It was found that the DLC film can be uniformly formed with an accuracy of 0.5 μm or less without being affected by the residence strain, and this process was found to be optimal.

In the semiconductor processed carrier member coated with the DLC film of the present invention, carbon is ion-implanted by 10 nm or more from the surface of the non-processed product, and a high-hardness DLC layer having a thickness of 1.0 to 10 μm is formed on the surface layer portion. This is a major feature. In the conventional plasma CVD method or PVD method, a DC voltage or an AC bias voltage of several tens to several hundreds of volts is generally applied to attract carbon ions in the plasma. Carbon atoms were not ion-implanted by 10 nm or more from the surface of the object, and it did not contribute to improving the adhesion to the substrate.

As a result of various changes in the pulse voltage, pulse width, repetition frequency, processing temperature, etc. of the negative voltage pulse, the deeper carbon atoms implanted from the surface of the workpiece contribute to improved adhesion. I found. As a result of the experiment, it is preferable that at least 10 nm or more of ions are implanted, and it has been found that if it is shallower than this, the contribution rate to the adhesiveness decreases.

When carbon atoms are implanted deeper than the surface layer portion and a hard DLC film having a thickness of 1 to 10 μm is formed on the surface thereof, a remarkable effect is exhibited in wear resistance, corrosion resistance, lubricity and contamination resistance. In such conventional plasma CVD method or a PVD method, the residual stress generated in the substrate interface, the carbon film is to 0.1~2.0μm deposited were common, 10 nm or more in the present invention As a result, the residual stress generated at the substrate interface was reduced, and a DLC film of 3.0 μm or more could be formed. According to experiments, it was found that, for example, a DLC film having a thickness of 50 to 100 μm can be formed on a flexible aluminum substrate, and can be applied as a sliding member having a high function and a long life.

Furthermore, what is important in the semiconductor processing carrier member is that impurities are not eluted during polishing of the silicon substrate . In semiconductor processing carrier members using conventional stainless steel, trace impurities such as iron, chromium and nickel are eluted, which may adversely affect the silicon substrate . With the semiconductor processed carrier member according to the present invention, it is possible to obtain a semiconductor processed carrier member in which the elution of impurities is not detected at all by the dense and uniform DLC film coating .

A semiconductor processing carrier member, which is a composite member of metal and plastic, is attached to a set frame. The set frame is integrated with a feedthrough for supplying high-frequency power. The high frequency power is fed to the semiconductor processing carrier member through the feedthrough and the set frame. By supplying high-frequency power to the semiconductor processing carrier member, high-density plasma is formed on the surface of the semiconductor processing carrier member . Ions, radicals, and electrons coexist in the plasma. When a negative voltage pulse is applied, high-energy carbon ions, hydrogen ions, and radicals are incident on the surface of the semiconductor processing carrier member, and ion implantation and chemical bonding are performed on the substrate surface. Thus, a DLC film is formed. By controlling the high frequency pulse and the negative voltage pulse, a desired combination of ion implantation and film formation becomes possible.

Embodiments of the present invention will be described below.
First, a schematic configuration of a plasma surface treatment apparatus used in an embodiment according to the present invention will be described with reference to FIG. This apparatus comprises a vacuum chamber 3 containing a set frame 2 on which a semiconductor processing carrier member 1 is set. The set base 2 also serves as an electrode for applying high-frequency power and a negative pulse voltage . The inside of the vacuum chamber 3 can be maintained at a predetermined degree of vacuum by the exhaust device 4. This apparatus has a hydrocarbon gas inlet 5 for introducing a predetermined hydrocarbon gas, and an organometallic gas inlet 6 for ion-implanting metal elements to improve the adhesion of the DLC film as required. I have.

The apparatus further includes a high voltage negative pulse power source 7 and a radio frequency (RF) power source 8 for applying a negative high voltage pulse to the semiconductor processing carrier member 1 having various shapes. The high voltage negative pulse power supply 7 generates a negative voltage pulse having a predetermined peak value and applies the negative voltage pulse to the semiconductor processing carrier member 1 through the high voltage feedthrough 9. This feedthrough is connected to the set base 2, and the set base 2 is held in an electrically floating state by an insulator 10. Further, at the time of DLC film formation, the negative voltage pulse and the high frequency power are superimposed by the superimposing device 11 and supplied to the semiconductor processing carrier member 1 through the high voltage feedthrough 9. A shield cover 12 is attached to the high voltage feedthrough 9 to protect the feedthrough 9.

A semiconductor processing carrier member 1 as shown in the A development view of FIG. 1 is set on the set base 2 of the present apparatus . Three to nine semiconductor processing carrier members 1 having a diameter of 500 mm and a thickness of 0.7 mm can be set on the gantry 2 . The semiconductor processing carrier member 1 has several openings a for fixing the silicon substrate , and a polyether resin ring 13 is bonded to the inner periphery of the opening . The shape of the opening and the resin material are arbitrarily selected. In addition, in order to accurately evaluate the film thickness after DLC film formation on a part of the member, the physical and chemical characteristics of the 10 × 10 × 0.3 mm square silicon test piece (b) and the DLC film-formed product are evaluated. A 25 × 25 × 2 mm square stainless steel test piece (c) is attached so that the test evaluation can be performed.

When a negative voltage pulse is applied to these semiconductor processed carrier members, carbon ions in the plasma or ions such as CH, CH _X and C ₂ are attracted to the semiconductor processed carrier member, and carbon ions or hydrogen ions are implanted. Since ions are implanted by applying a negative voltage pulse to a semiconductor processing carrier member, an electric field is generated along the shape of the member even if the member is not a flat plate but an uneven solid shape, and is almost perpendicular to the surface. Carbon ions are incident . Therefore if there are irregularities in the plastic member is an insulating it is possible to inject carbon ions across the plastic surface is also. At the same time, hydrogen ions are also ion-implanted, but it is known that hydrogen in the base material diffuses and degass after injection, and it is considered that the physical properties of the base material are not greatly affected. .

After the carbon ion implantation, a DLC film is continuously formed. Although the carbon ion implantation is preferably not less than several kV is ion implanted at a voltage higher than 10 kV, the formation of the DLC film methane, acetylene, benzene, 10 kV or less gas to hydrocarbon gas was mixed in any proportion, such as toluene The film is formed while applying a negative voltage pulse of. This is because when the DLC film is formed at a high energy, the film structure of the DLC is disturbed by the collision energy of ions, and it is difficult to obtain a hard and high-grade film, and it is difficult to obtain a film formation speed. In particular, it is preferable to form a film with lower energy as the surface layer portion is obtained because a high-quality DLC film-coated article is obtained. It is preferable to use a film forming technique in which the voltage is gradually lowered from the high voltage side to the low voltage side by automatic control during film formation.
This will be described below based on examples.

(Experimental example 1)
Using the plasma surface treatment apparatus shown in FIG. 1, a plurality of analytical test pieces b and c are pasted in the vicinity of the opening a provided in the semiconductor processing carrier member 1 as shown in an A development view in FIG. Used for analytical evaluation. In the experiment, plasma was generated under the following conditions, and carbon ion implantation + DLC film was formed and evaluated.

Material used: Stainless steel (SUS304 made by Nippon Steel & Sumikin Stainless Steel)
Use gas type: Methane gas / acetylene mixed gas mixing ratio: Methane gas 50 / acetylene 50
Pressure during injection / film formation: 0.5 Pa to 1.0 Pa
Negative voltage pulse during injection: 10 kV, 20 kV, 30 kV
Negative voltage pulse during film formation: 10 kV → 2 kV
Injection time: 30 minutes Carbon film formation time: 180 minutes Application frequency: 2000 Hz

The negative voltage pulse during the injection under the above three conditions was applied to inject carbon ions into the stainless steel, and then the DLC film was formed using methane / acetylene mixed gas plasma while the voltage was lowered. The deposition time pressure, since the film forming time is causing the gas pressure change a negative voltage pulse fluctuate, represents the pressure range at that time, the arrow of the pulse voltage while low reducing a pulse voltage to the film forming time It shows that it experimented. The distribution of the implanted carbon element in the depth direction was evaluated by an Auger analyzer (AES), and the carbon implantation depth and amount (atomic%) were determined. Further, the hardness and adhesion of the stainless steel substrate surface were measured with a dynamic hardness meter and a scratch adhesion evaluation tester, and the friction coefficient was measured with a steel ball in a friction test by a ball and disk method. The DLC film thickness was determined by obtaining the DLC film thickness attached to the silicon test pieces attached to nine locations of the semiconductor processing carrier member , and evaluating variations in the DLC film thickness. FIG. 2 shows carbon injection distributions at injection energies of 10 keV, 20 keV, and 30 keV by AES analysis. The hardness, adhesion, and friction coefficient are shown in FIG. 3 in comparison with untreated stainless steel.

FIG. 2 shows the relationship between the carbon implantation depth and the carbon concentration by Auger analysis of a film in which carbon ion implantation and a DLC film are formed on a SUS304 substrate. The horizontal axis indicates the depth direction of the stainless steel substrate, and the origin indicates the DLC film material surface . The vertical axis represents the proportion of carbon atoms in the material. In the analysis, the DLC film was analyzed in advance by removing surface contaminants by argon sputtering. As can be seen from FIG. 2, the carbon layer, which is the main component of the DLC film, is formed up to about 300 nm on the stainless steel surface, and the vicinity of 330 nm is seen as the outermost layer portion of the stainless steel. From this, it can be seen that the carbon injection layer is a high-concentration carbon layer from 380 nm to about 450 nm. As a result, it can be seen that the higher the implantation energy, the deeper the carbon penetration depth, and the ion implantation into the interior. It can be seen that the carbon implantation depth is about 10 nm at 10 keV, 90 nm at 20 keV, and 120 nm at 30 keV. This shows that the higher the applied voltage before forming the DLC film , the deeper the carbon is injected into the stainless steel material, and the inclined structure is formed.

On the other hand, the dynamic hardness, scratch adhesion and friction coefficient of the stainless steel surface are shown in FIG. Untreated stainless steel is very soft with a hardness of 570, but by forming a DLC film, all show a hardness of 1300 or more, and the scratch adhesion also shows an adhesion of 15 N or more despite the soft substrate. I understand that. Stainless steel exhibited a very high coefficient of friction of 0.3 or more, but all of the DLC films exhibited a low coefficient of friction of 0.18 or less. Looking at the relationship with the ion implantation energy, it was found that at a suitable implantation energy, the hardness was high and the friction coefficient was low. Furthermore, as a result of evaluating the uniformity of the DLC film thickness, as a result of measuring 9 points for each of the six semiconductor processed carrier members as shown in FIG. 3, the DLC film can be formed with an average film thickness of 2 μm ± 0.3 μm. I understood.

(Experimental example 2)
Using the plasma surface treatment apparatus shown in FIG. 1 , a plurality of analytical test pieces b and c are provided in the vicinity of the opening a provided in the titanium alloy semiconductor processing carrier member 1 as shown in an A development view in FIG. Used for pasting and analysis evaluation. In the experiment, plasma was generated under the following conditions, and carbon ion implantation + DLC film was formed and evaluated.

Material used: Titanium alloy material (KS6-4 manufactured by Kobe Steel, Ltd.)
Gas type used: Acetylene / toluene gas mixture ratio: Acetylene 70 / toluene 30
Pressure during injection / film formation: 0.5 Pa to 1.0 Pa
Negative voltage pulse during injection: 10 kV, 20 kV, 30 kV
Negative voltage pulse during film formation: 10 kV → 2 kV
Implantation time: 30 minutes Carbon film formation time: 180 minutes Application frequency: 3000 Hz

The negative voltage pulse during the injection under the above three conditions was applied to inject carbon ions into the titanium alloy plate, and subsequently a DLC film was formed in an acetylene / toluene mixed gas plasma while reducing the pulse voltage. The distribution of the implanted carbon atoms in the depth direction was evaluated by an Auger analyzer (AES), and the implantation depth and amount of carbon atoms were determined. Further, the hardness and adhesion evaluation of the titanium alloy substrate surface were measured using a dynamic hardness meter and a scratch adhesion evaluation tester . Furthermore, the coefficient of friction was measured using a steel ball in a ball and disk friction test. The thickness of the DLC was measured by measuring the thickness of the DLC film deposited on the silicon test pieces attached to nine locations of the semiconductor processing carrier member , and evaluating the variation in the DLC film thickness. FIG. 5 shows carbon injection distributions at injection energies of 10 keV, 20 keV, and 30 keV by AES analysis . Further, the hardness, adhesion, and coefficient of friction are shown in FIG. 6 in comparison with an untreated titanium alloy.

FIG. 4 shows the results of Auger analysis. The horizontal axis indicates the depth from the DLC film surface, and the origin indicates the DLC film surface. The vertical axis represents the proportion of carbon atoms in the material. It can be seen that a DLC film is formed from the surface to a depth of 330 nm, and the carbon injection layer to the titanium alloy substrate is from 330 nm to around 420 nm to 540 nm. As a result, it can be seen that the higher the implantation energy, the deeper the carbon penetration depth, and the ion implantation into the interior. It can be seen that the carbon implantation depth is about 10 nm at 10 keV, about 160 nm at 20 keV, and about 200 nm at 30 keV. This shows that the higher the negative pulse voltage before the DLC film is formed , the deeper the carbon enters the titanium alloy base material, and the inclined structure is formed .

On the other hand, FIG. 5 shows the dynamic hardness, scratch adhesion and friction coefficient of the surface-treated titanium alloy surface . The untreated titanium alloy is very soft with a hardness of 320, but any of them exhibits a hardness of 1100 or more by forming a DLC film . It can be seen that the scratch adhesion also shows an adhesion of 12 N or more despite the soft substrate. Titanium alloys showed a very high friction coefficient of 0.4, but all showed a low friction coefficient of 0.16 or less by the DLC film. Looking at the relationship with ion implantation energy, it was found that the hardness tends to be slightly lower at higher energies.
Further, as a result of evaluating the uniformity of the DLC film thickness, as shown in FIG. 5, as a result of measuring 9 positions on each of the six semiconductor processed carrier members , an error range of ± 0.3 μm with respect to the average film thickness of 2 μm. It was found that DLC film formation was possible.

Although not described in the experimental examples , the same experiment and evaluation were performed on the glass epoxy base material. As a result, carbon ion implantation was confirmed up to about 130 nm with 10 keV energy, and DLC formed with acetylene / toluene. It was found that the physical properties after film formation were similar to those of the titanium alloy. Thus metal, pulsed ion implantation and the DLC deposition followed by carbon regardless of insulating material was found to be essential.

As described above, by applying the carbon ion implantation to the semiconductor processing carrier member using the surface treatment method according to the present invention and further forming the DLC film on the surface, the wear resistance and corrosion resistance of the semiconductor processing carrier member are obtained. It has been found that a DLC-coated article excellent in stain resistance and a surface treatment method thereof can be provided.

Further, since the DLC-coated article by the surface treatment method according to the present invention has high surface hardness and excellent wear resistance, corrosion resistance, and contamination resistance, aluminum magnetic disk substrates and glass magnetic disks other than those in the semiconductor industry field It can also be used for polishing substrates, glass substrates for photomasks, crystal oscillators, optical lenses, and reflecting mirrors. Furthermore, the carbon ion implantation + DLC film forming technology of the present invention can increase lubricity, water repellency, and release properties in addition to wear resistance, corrosion resistance, and contamination resistance. The present invention can also be applied to industrial ceramic materials and metal material molded products such as increasing the surface hardness of ceramic materials and improving the functionality of lubricity and releasability.

It is a schematic block diagram of the plasma surface treatment apparatus used for the Example which concerns on this invention. It is a figure which shows the relationship between the carbon implantation depth by the Auger analysis after carbon ion implantation + DLC formation to SUS304, and a carbon concentration. It is a table | surface which shows physical changes, such as the hardness after carbon ion implantation + DLC formation to SUS304, adhesion, and a friction coefficient, and film thickness distribution. It is a figure which shows the relationship between the carbon implantation depth by the Auger analysis after carbon ion implantation + DLC formation to a titanium material, and carbon concentration. It is a table | surface which shows physical changes and film thickness distribution, such as the hardness after carbon ion implantation to DLC + DLC formation, adhesive force, and a friction coefficient.

DESCRIPTION OF SYMBOLS 1 Semiconductor carrier member 2 set mounting frame 3 Vacuum chamber 4 Exhaust device 5 Hydrocarbon gas inlet 6 Organometallic gas inlet 7 High voltage negative pulse power source 8 High frequency (RF) power source 9 High voltage feedthrough 10 Insulator 11 Superposition device 12 Shield cover

Claims (6)

A semiconductor processing carrier member comprising a metal member and at least one resin member selected from polyimide resin, polyamideimide resin, polyetheretherketone resin, nylon resin, glass fiber reinforced epoxy resin and carbon fiber reinforced epoxy resin Installed in a plasma surface treatment apparatus, introduces a hydrocarbon-based gas into the plasma surface treatment apparatus, maintains the gas pressure at 0.1 to 10 Pa, and feeds high-frequency power to the semiconductor processing carrier member A discharge plasma is generated, a negative high voltage pulse having a pulse voltage of 1 to 50 kV and a frequency of 100 to 5000 cycles is applied to the semiconductor processed carrier member, and carbon ions are implanted into the surface of the semiconductor processed carrier member. and forming a diamond-like carbon layer on a semiconductor The surface treatment method of engineering the carrier member. As the hydrocarbon gas, carbon ions are injected using at least one gas selected from the gas group consisting of methane, acetylene, benzene, toluene, cyclohexane, chlorobenzene, carbon difluoride, and carbon tetrafluoride. 2. A surface processing method for a semiconductor processing carrier member according to claim 1, wherein a diamond-like carbon layer is formed on the surface of the semiconductor processing carrier member. The voltage of the negative high voltage pulse applied to the semiconductor processing carrier member is a 10KV～30kV, semiconductor processing according to claim 1 and 2 carbon ion implantation time is characterized in that 30 to 120 minutes A surface treatment method for a carrier member. The surface treatment method for a semiconductor processing carrier member according to any one of claims 1 to 3, wherein the metal member is stainless steel or a titanium alloy . After carbon ion implantation into the semiconductor processing carrier member surface, to continue to form a diamond-like carbon layer of a thickness of at least 1 [mu] m, from claim 2, characterized in that the friction coefficient of the surface to 0.18 4 The surface treatment method of the semiconductor processing carrier member in any one of. The semiconductor processing carrier article manufactured using the surface treatment method in any one of Claim 1 to 5 .

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