JP4751198B2 - Components for plasma processing equipment - Google Patents

Description

  The present invention relates to a member for a plasma processing apparatus that constitutes a plasma processing apparatus that performs film formation, etching, and the like for manufacturing semiconductors and liquid crystals.

  Conventionally, many aluminum members have been used as members constituting a plasma processing apparatus that performs film formation, etching, and the like for manufacturing semiconductors and liquid crystals. In particular, as shown in FIG. 2, in the plasma processing apparatus (CVD apparatus) 10, the upper electrode 12 and the lower electrode 13 installed in the upper and lower portions of the processing chamber 11 are required to have high corrosion resistance. Since the surface state of the electrode greatly affects the uniformity and stability of the process, various contrivances such as control of the mechanical shape and control by surface treatment are performed on the surface.

  In the plasma processing apparatus (CVD apparatus) 10, a work W such as a wafer or a glass substrate is directly placed on the lower electrode 13. Then, when the film forming process for the workpiece W is completed, the knock pins 16 rising through the holes 15 provided at several positions on the outer peripheral end of the lower electrode 13 lift the workpiece W above the lower electrode 13 and lift it. The workpiece W thus taken out is taken out from the processing chamber 11 by a robot hand (not shown) or the like. When the workpiece W is lifted by such a knock pin 16, so-called “sticking” in which the workpiece W is not separated from the lower electrode 13 by electrostatic adsorption may occur. The occurrence of such sticking leads to breakage of the knock pin 16 and eventually breakage of the work W. Therefore, in order to prevent sticking, the surface of the lower electrode 13 may be subjected to blasting or the like.

Such a blasting process is described in Patent Document 1, and in this blasting method, a protruding sharp tip is formed on the surface of the lower electrode 13 and is generated due to wear with the workpiece (wafer) W. The solid particles that cause contamination of impurities, and in addition, the contact ratio between the lower electrode 13 and the wafer W increases due to the progress of wear of the lower electrode 13, and the heat conduction from the lower electrode 13 to the wafer W changes. It describes that it adversely affects the process conditions of the film of the wafer W. A method of polishing the surface of the lower electrode 13 by chemical etching for the purpose of removing a sharp tip after blasting is proposed, and the contact area between the lower electrode 13 and the wafer W is reduced by this polishing process. It is described that the electrostatic attraction force is reduced and sticking is prevented. Japanese Patent Application Laid-Open No. H10-228561 also describes that a lathe is provided with irregularities such as a corrugated shape on the surface of the lower electrode 13 to reduce the contact area with the wafer W and prevent sticking.
Japanese Patent No. 3160229 (paragraphs 0008 to 0010, 0021, 0025, FIG. 2) JP-A-8-70034 (Claim 5, paragraph 0016, FIG. 10)

  However, in the case of the lower electrode 13, when blasting is performed as in Patent Document 1, residual stress is inevitably generated in the lower electrode 13, the lower electrode 13 warps, and the wafer W may not be stably held. Further, if the surface of the lower electrode 13 is patterned into a corrugated shape or the like as in Patent Document 2, film formation unevenness may occur on the wafer W along the pattern of the lower electrode 13. Therefore, the member for plasma processing apparatus of Patent Document 1 or 2 subjected to the blasting process or the surface patterning process is not excellent in the sticking resistance and performance required for the lower electrode 13.

  Further, in a member for a plasma processing apparatus typified by the lower electrode 13 and the upper electrode 12, in a state where static electricity is held on the member, it is locally applied to an electrically weak portion such as a minute defect of the member during the plasma process. There is also a risk that electricity concentrates on the surface, causing problems such as abnormal discharge.

  An object of the present invention is to solve the above-mentioned problems, and to provide a member for a plasma processing apparatus that has excellent anti-sticking properties and can suppress abnormal discharge during a plasma process.

In order to solve the above problems, the invention described in claim 1 is a member for a plasma processing apparatus that constitutes a plasma processing apparatus for performing plasma processing on a workpiece, and comprises a substrate made of aluminum or an aluminum alloy, and the base And an anodic oxide film having a thickness of 3 μm or more formed only on the surface of the material, and the anodic oxide film has a leakage current density of 0.9 × 10 ⁻⁵ (A / It is constituted as a member for a plasma processing apparatus exceeding cm ² ).

According to the said structure, corrosion resistance is provided to the member for plasma processing apparatuses by providing an anodic oxide film on the surface of a base material. In addition, since the anodized film has a predetermined leakage current density, the charge on the plasma processing apparatus member is reduced during the plasma process such as semiconductor film formation on the workpiece surface, and the workpiece is statically applied to the member surface. Electroadsorption is suppressed, and the charge distribution of the plasma processing apparatus member becomes uniform, and the portion where it is electrically concentrated is reduced. Moreover, when the anodic oxide film has a predetermined film thickness, chemical resistance to acid, alkali, and gas corrosion resistance are imparted to the member for a plasma processing apparatus.

The invention according to claim 2 is a member for a plasma processing apparatus that constitutes a plasma processing apparatus that performs plasma processing on a workpiece, and comprises a base material made of aluminum or an aluminum alloy, and an anodized surface on the surface of the base material processing a said anodized hot water immersion sealing treatment and the film thickness formed by the 3μm or more of the anodized film by performing after treatment, the anodized film, at least a part of the anodized film is boehmite And / or pseudo boehmite, which is configured as a member for a plasma processing apparatus having a leakage current density exceeding 0.9 × 10 ⁻⁵ (A / cm ² ) at an applied voltage of 100V .

The above configuration can be realized by sealing treatment by hot water immersion , and the leakage current density of the anodic oxide film can be controlled by fine cracks introduced by the sealing treatment, so that it has a more preferable leakage current density, and plasma treatment is performed. The charge on the device member is reduced, and the charge distribution is more uniform. Further, in the sealing treatment by hot water immersion, excessive expansion of the film in the vicinity of the surface of the anodized film is suppressed, and cracks that propagate to the entire film thickness are less likely to occur.

The member for a plasma processing apparatus according to the present invention is excellent in sticking resistance when used as a lower electrode of a plasma processing apparatus, and also when used for a lower electrode, an upper electrode or other members of a plasma processing apparatus. Abnormal discharge during the plasma process can be suppressed. In addition, chemical resistance to acid, alkali, etc., and gas corrosion resistance are excellent.

Embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing the structure of a member for a plasma processing apparatus, and FIG. 2 is a cross-sectional view schematically showing the structure of a CVD apparatus.
The present invention is a member for a plasma processing apparatus that constitutes a plasma processing apparatus that performs plasma processing on a workpiece. The plasma processing apparatus is an apparatus used in a semiconductor or liquid crystal manufacturing process (film formation, etching, etc.) such as a dry etching apparatus, a CVD apparatus, a PVD apparatus, an ion implantation apparatus, and a sputtering apparatus.

  As shown in FIG. 2, a CVD apparatus 10 that is a typical plasma processing apparatus includes a processing chamber 11 having a predetermined internal space, an upper electrode 12 disposed so as to face the processing chamber 11, and And a lower electrode 13. The upper electrode 12 is disposed on the upper portion of the processing chamber 11 and connected to a gas inlet (not shown). The lower electrode 13 is supported by a lower electrode support arm 14 at the lower portion of the processing chamber 11. Further, the lower electrode 13 has holes 15 formed at the end thereof at predetermined intervals (for example, when the lower electrode 13 has a disk shape, 3 to 4 locations on the outer peripheral end). Further, a knock pin 16 is inserted into the pinhole 15.

  In the CVD apparatus 10, a source gas (for example, a mixed gas of tetraethylorthosilicate and oxygen gas) is evacuated from the gas inlet (not shown) through the upper electrode 12 into the processing chamber 11. be introduced. The lower electrode 13 and the workpiece (wafer, glass) W placed on the surface thereof are heated to a predetermined temperature by a heater (not shown) built in the lower electrode 13 or fastened by a bolt or the like. Then, the inside of the processing chamber 11 is maintained at a reduced pressure and a predetermined high frequency power is applied to the upper electrode 12 to generate plasma between the upper electrode 12 and the lower electrode 13. As a result, a semiconductor film (for example, a silicon oxide film) having a predetermined thickness grows on the wafer W. The wafer W after film formation is separated (lifted) from the lower electrode 13 by raising the knock pin 16 in the hole 15 and taken out from the processing chamber 11 by a robot hand (not shown) or the like.

  The plasma processing apparatus member of the present invention is preferably used as a member constituting the upper electrode 12 and the lower electrode 13 in the CVD apparatus 10 described above, but is not limited to the upper electrode 12 and the lower electrode 13. The CVD apparatus 10 may be used as, for example, a member constituting the processing chamber 11, the knock pin 16, and the like.

Next, the structure of the plasma processing apparatus member of the present invention will be described.
As shown in FIG. 1, the plasma processing apparatus member 1 includes a base material 2 made of aluminum or an aluminum alloy, and an anodized film 3 formed on the surface of the base material 2. Each configuration will be described below.
(Base material)
The aluminum or aluminum alloy used as the base material 2 is not particularly limited, but from the viewpoint of having sufficient mechanical strength, thermal conductivity, and electrical conductivity as a member for a plasma processing apparatus, a JIS-defined 3000 series alloy (Al-Mn series) Alloy), 5000 series alloy (Al-Mg based alloy), or 6000 series alloy (Al-Mg-Si based alloy) is preferable.

  Although the form of the base material 2 changes with the usage location of the member 1 for plasma processing apparatuses, it is preferable that they are a rolling material, an extrusion material, or a forging material. Therefore, the base material 2 is produced by a conventionally known rolling method, extrusion method or forging method.

(Anodized film)
The anodized film 3 is a cell assembly having a hexagonal column-shaped cell 7 having a pore (hole) 4 in the center as a basic structure, and a porous layer (portion 4 is formed) 5 and a barrier layer. (A layer having no pore 4 interposed between the porous layer 5 and the substrate 2) 6 is a composite film. Moreover, it is preferable that at least a part of the anodized film 3 is boehmite and / or pseudoboehmite. In addition, by forming such an anodized film 3 on the surface of the substrate 2, gas corrosion resistance is imparted to the member 1 for plasma processing apparatus according to the present invention. Here, the surface of the base material 2 includes not only the entire surface of the base material 2 but also the surface on which the anodized film 3 is formed only on a part thereof. For example, when the plasma processing apparatus member 1 is used as the lower electrode 13 of the CVD apparatus 10 as shown in FIG. 2, it is sufficient that the anodized film 3 is formed on at least the surface in contact with the wafer W. .

In the present invention, an appropriate leakage current is generated in the anodic oxide film 3, and the leakage current density is adjusted to a predetermined range. Specifically, the leakage current density at an applied voltage of 100 V is 0.9 × 10 ^−5. It adjusts so that it may exceed (A / cm < ² >). Since the anodized film 3 has such a leakage current density, when the plasma processing apparatus member 1 according to the present invention is used as the lower electrode 13 of the CVD apparatus 10 as shown in FIG. It becomes possible to suppress sticking. Further, when the plasma processing apparatus member 1 is applied to the upper electrode 12, the lower electrode 13, or another member, it is possible to suppress abnormal discharge during the plasma process. When the leakage current density is 0.9 × 10 ⁻⁵ (A / cm ² ) or less, the effect is lowered. From the standpoint of sticking resistance, the upper limit of the leak current density is not particularly defined. However, if the leak current density exceeds 20 × 10 ⁻⁵ (A / cm ² ), the gas corrosion resistance is lowered. The density is preferably more than 0.9 × 10 ⁻⁵ (A / cm ² ) and not more than 20 × 10 ⁻⁵ (A / cm ² ).

  That is, in the CVD apparatus 10, when the lower electrode 13 is configured by the plasma processing apparatus member 1 according to the present invention, the charge charged to the lower electrode 13 during the semiconductor film forming process on the surface of the wafer W is caused by fine cracks in the anodized film. Is discharged and its charge decreases. As a result, after the semiconductor film forming process, electrostatic adsorption to the lower electrode 13 of the wafer W is suppressed, and sticking does not occur when the wafer W is removed. Further, when the upper electrode 12, the lower electrode 13 or another member is constituted by the plasma processing apparatus member 1, the charge charged to the plasma processing apparatus member 1 is discharged from the fine cracks of the anodized film, and the electrode or member is electrically charged. Therefore, the concentrated portion is reduced and the charge distribution becomes uniform. Therefore, it is possible to suppress so-called abnormal discharge, which is caused by concentration of electricity in an electrically weak part during the plasma process, and to improve plasma uniformity.

  The leakage current density can be controlled by controlling the thickness and structure of the anodic oxide film 3. When the leakage current density of the anodic oxide film 3 is controlled only by the film thickness, the film thickness is preferably less than 10 μm. When the film thickness is 10 μm or more, it is difficult to control the leakage current density only by controlling the film thickness. However, even when the film thickness is less than 10 μm, it is more preferable to perform the following structure control of the anodic oxide film 3 in order to more stably control the variation of the leak current value. Moreover, it is preferable to control the film thickness of the anodic oxide film 3 to 3 μm or more from the viewpoint of chemical resistance to acids, alkalis and the like and gas corrosion resistance. Therefore, it is more preferable to control the structure of the anodic oxide film 3 below by controlling the film thickness to 3 μm or more. On the other hand, if the film thickness exceeds 120 μm, the film thickness becomes too thick and the anodic oxide film 3 is liable to peel off due to the influence of internal stress and the like. Therefore, the film thickness is more preferably 3 to 120 μm, and the optimum film thickness is 10 to 70 μm. The film thickness is controlled by controlling the conditions of anodizing treatment described later.

The structure control of the anodized film 3 is to control the density and distribution of cracks generated in the anodized film 3 in order to achieve both leakage current generation and gas corrosion resistance. It is something to avoid. Such control is performed when at least a part of the anodized film 3 is converted to boehmite and / or pseudoboehmite by hydration treatment (sealing treatment) of the anodized film 3 described later. Here, whether or not a part of the anodic oxide film 3 is converted to boehmite and / or pseudoboehmite is confirmed by the dissolution rate of the anodic oxide film 3 in the phosphoric acid-chromic acid aqueous solution immersion test (JISH 8683-2). Can do. Then, can be regarded as the dissolution rate of the anodic oxide film 3 is not more than 100 mg / dm ² / 15min, a part of the anodized film 3 is boehmite and / or pseudo boehmite. Such boehmite and / or pseudoboehmite can be controlled by controlling the conditions of hydration treatment (sealing treatment).

The anodizing method for forming the anodic oxide film 3 having the leakage current density and the hydrated oxide on the surface of the substrate 2 is as follows.
In the anodizing treatment, an aluminum alloy is immersed in an electrolytic solution, a voltage is applied, and an aluminum oxide film is formed on the surface of the aluminum alloy by utilizing an oxidation phenomenon caused by oxygen generated at the anode. Various methods such as a direct current method, an alternating current method, and an AC / DC superposition method are used as the energization method for the anodizing treatment.

  Electrolytic solutions for anodizing treatment are not particularly limited, but inorganic acid solutions such as sulfuric acid solution, phosphoric acid solution, chromic acid solution, boric acid solution, organic acid solutions such as formic acid solution and oxalic acid solution, and mixtures thereof Illustrated.

  The electrolytic voltage during the anodizing treatment is not particularly limited, and may be appropriately controlled according to the film growth rate, the electrolytic solution concentration, and the like. For example, when an oxalic acid solution is used, the film hardness may be reduced if the electrolytic voltage is low. In addition, a sufficient film growth rate cannot be obtained, and the anodic oxidation efficiency deteriorates. On the other hand, when the electrolysis voltage is high, the anodized film 3 is easily dissolved, and the anodized film 3 may be defective. Therefore, the electrolysis voltage is preferably 10 V or more and 120 V or less, more preferably 15 V or more and 100 V or less. Furthermore, it does not specifically limit as anodizing time, What is necessary is just to determine processing time, calculating suitably the time which can obtain the film thickness of the desired anodic oxide film 3. FIG.

  In the present invention, in order to generate a leakage current, it is preferable to perform a hydration treatment (sealing treatment) in which the anodized film 3 (porous layer 5) is brought into contact with high-temperature water after the anodizing treatment. Examples of the hydration treatment method include a method in which the anodic oxide film 3 is immersed in hot water (hot water immersion), or a method in which it is exposed to water vapor. In the case of hydration treatment by exposure to water vapor, the treatment conditions may be appropriately adjusted so that the water can be hydrated, for example, the water vapor is heated to a high temperature (for example, 100 ° C. or higher). However, if the film expansion near the film surface proceeds excessively, cracks that propagate to the entire film thickness may occur. As a result, the gas corrosion resistance of the plasma processing apparatus member 1 is reduced. Therefore, it is necessary to precisely control the temperature and treatment time during the hydration treatment. In particular, in the hydration treatment exposed to water vapor, more precise control is required, so hydration treatment by hot water immersion is recommended. The temperature and treatment time of hot water (boiling water) immersion are appropriately determined depending on the type of electrolytic solution for anodizing treatment, the film thickness of the anodized film 3, and the conditions for generating cracks in the anodized film 3. ˜100 ° C. × 5 to 310 minutes is preferable, and 80 to 100 ° C. × 5 to 60 minutes is more preferable.

Next, examples of the present invention will be described.
An anodized film is formed on the surface of the aluminum base material by subjecting the aluminum base material made of JIS standard 6061 alloy and 5052 alloy to anodizing treatment (the direct current method is a direct current method) and sealing treatment under the conditions shown in Table 1. A sample was prepared. About the obtained test material, the dissolution rate of the anodic oxide film by the leakage current density and the phosphoric acid-chromic acid aqueous solution immersion test was measured with the measuring method shown below. Here, in Examples 1 to 6, 8, 9, and 11 to 15, anodizing treatment and sealing treatment were performed, and in Examples 7, 10 and Comparative Examples 1 to 4, only anodizing treatment was performed, and sealing treatment was performed. Did not do.

(Measurement of leakage current density)
A test piece (50 × 50 × 5 mm) was prepared from the test material, and about 1 μm of aluminum was deposited on the anodized film surface of the test piece to form an electrode of about 1 cm square for measurement. And the leakage current density in the applied voltage 100V was measured using the commercially available current voltage measuring device. The results are shown in Table 2.

(Measurement of dissolution rate)
JISH8683-2 the specimen phosphate based on 1999 - after immersion in chromic acid solution, measuring the weight loss of the test piece before and after the immersion was calculated dissolution rate ^{(mg / dm 2 / 15min)} . As described in JISH 8683-2 1999, the test piece was immersed in an aqueous nitric acid solution (500 mL / L, 18 to 20 ° C.) for 10 minutes, then the test piece was taken out, washed with deionized water, and dried in warm air. Then, the mass was measured. Next, the test piece was immersed in an aqueous solution of phosphoric acid-chromic anhydride (phosphoric acid 35 mL, 20 g of anhydrous chromic acid dissolved in 1 L of deionized water) maintained at 38 ± 1 ° C. for 15 minutes. The test piece was taken out, washed in a water bath, washed thoroughly in running water, further washed in deionized water and dried with warm air, and then the mass was measured to calculate the mass reduction per unit area. The results are shown in Table 3. Here, the dissolution rate is equal to or less 100 mg ^/ dm 2 / 15min, can be regarded as part of the anodized film is boehmite and / or pseudo boehmite.

  Next, the following tests were performed using the above-mentioned test materials, and the sticking resistance and the suppression of abnormal discharge were evaluated. The results are shown in Table 2.

(Sticking resistance test)
A lower electrode 13 (φ250 mm) of the CVD apparatus 10 as shown in FIG. 2 is prepared from the test material, and 100 wafers (φ200 mm) are processed using the CVD apparatus 10 to investigate the occurrence of sticking. . In sticking, the knock pins 16 are lifted from four positions (four positions every 90 degrees) of the lower electrode 13 to visually determine whether the wafer W is peeled off from the lower electrode 13 smoothly. As a result of this test, “O” indicates that no sticking of the wafer W occurs at all, and “Good” indicates that the sticking resistance is excellent. [Delta] "Each of the five or more wafers W that was sticking was evaluated as" x "as having poor sticking resistance.
The CVD apparatus 10 cleans the inside of the processing chamber 11 using the source gas, and then heats the lower electrode 13 and the wafer W placed on the lower electrode 13 to 300 to 380 ° C., and about 2 to In the processing chamber 11 maintained at a reduced pressure of 5 Torr (about 260 to 670 Pa), a plasma was generated to generate a silicon oxide film of about 500 nm on the surface of the wafer W.

(Abnormal discharge test)
An upper electrode 12 (φ250 mm) of the CVD apparatus 10 as shown in FIG. 2 is produced from the test material, and 100 wafers (φ200 mm) are processed using the CVD apparatus 10 in the same manner as the sticking resistance test. The presence of abnormal discharge was investigated. The evaluation of suppression of abnormal discharge was performed simultaneously with the sticking test, and the presence or absence of brown to black spot marks of about 0.1 to 1 mm on the upper electrode 12 was visually determined. As a result of the test, “◯” indicates that there is no point-like trace at all, and “◯” indicates that it is excellent in suppressing abnormal discharge. Those having 3 or more marks were evaluated as “x” as being inferior to suppression of abnormal discharge.

From the results of Tables 1 to 3, Examples 1 to 15 were excellent in sticking resistance and suppression of abnormal discharge in order to satisfy the claims. Moreover, since Comparative Examples 1-4 did not satisfy the claim, it was inferior to sticking resistance and suppression of abnormal discharge. Further, from the results shown in Table 3, in Example 1～6,8,9,11～15, dissolution rate of the anodic oxide film is less than or equal to 100 mg / dm ² / 15min, a part of the anodized film boehmite and / or It was confirmed to be pseudo boehmite. Then, Example 7, Example 10, Comparative Examples 1 to 4, at a rate of dissolution of the anodized film is 100 mg / dm ² / 15min or more, it confirmed that the anodized film is not boehmite and / or pseudo boehmite It was done.

It is sectional drawing which shows typically the structure of the member for plasma processing apparatuses which concerns on this invention. It is sectional drawing which shows the structure of a CVD apparatus typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plasma processing apparatus member 2 Base material 3 Anodized film 4 Pore 5 Porous layer 6 Barrier layer 7 Cell

Claims (2)

A plasma processing apparatus member constituting a plasma processing apparatus for performing plasma processing on a workpiece,
A substrate made of aluminum or an aluminum alloy;
An anodized film having a thickness of 3 μm or more formed only on the surface of the base material by anodization ;
The member for a plasma processing apparatus, wherein the anodic oxide film has a leakage current density exceeding 0.9 × 10 ⁻⁵ (A / cm ² ) at an applied voltage of 100V. A plasma processing apparatus member constituting a plasma processing apparatus for performing plasma processing on a workpiece,
A substrate made of aluminum or an aluminum alloy;
An anodized film having a thickness of 3 μm or more formed on the surface of the base material by anodizing treatment and sealing treatment by hot water immersion performed after the anodizing treatment;
The anodized film, I at least partially boehmite and / or pseudoboehmite der of the anodized film, the leak current density at applied voltage 100V exceeds ^{0.9 × 10 -5 (A / cm} 2) A member for a plasma processing apparatus, wherein the member is a member.

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