TWI577647B - Surface treatment for quartz materials, composition for surface treatment of quartz materials and quartz materials manufactured by the same - Google Patents

Description

Surface treatment method of quartz raw material, composition for surface treatment, and quartz raw material prepared thereby

The present invention relates to a surface treatment method for a quartz raw material, a composition for surface treatment, and a quartz raw material produced thereby, and more particularly to a physical etching process caused by sand blasting in the process of processing the surface of a quartz raw material. The surface treatment method, the surface treatment composition, and the surface treatment method of the quartz raw material in which the uniform and fine indented irregularities are easily obtained by the inner treatment of the tube, the large-scale treatment, and the chemical etching capable of producing a plurality of members. Made of quartz raw materials.

Quartz products are widely used in semiconductors because of their high purity (99.999%), chemical stability, acid resistance, heat resistance (softening point temperature of 1683 ° C), excellent light transmission, and low thermal expansion and electrical insulation. Optical communications, electrical appliances, electronics and other industries.

For example, in the processing of the ruthenium sheet, the ruthenium sheet is usually processed by a process such as vapor deposition (CVD), etching, or ashing, and a quartz product is used in such a process in order to support or arrange the wafer.

In this case, since a high temperature of 1000 ° C or more is applied to such a process, a stress caused by a difference in thermal expansion coefficient between the quartz and the tantalum sheet is generated in a portion where the wafer and the quartz surface are in contact with each other, and the contact can be made at the above contact. Partially made contact marks.

Further, when the substance generated in the processing step of the bismuth sheet adheres to the surface of the quartz raw material product to form a film, when the quartz raw material product is cooled after the treatment process, the film and the film may be as described above. The difference in thermal expansion coefficient between the glass The quartz raw material product is cracked or broken.

Further, in the case where the above-mentioned quartz raw material product is cooled as described above, if the state of adhesion of the substance on the surface of the quartz is weak, the substance is detached from the surface of the quartz, but if the roughness of the surface of the quartz is small The adhesion state is further strengthened, and the film remains in the subsequent treatment process of the ruthenium sheet, and even if cracking or damage does not occur in the quartz raw material product, particles can be formed before the film is detached from the surface.

In order to avoid the occurrence of the above-described contact marks and to reduce the contact area on the wafer, a sand blast treatment is performed on the surface of the quartz raw material product, so that the surface of the quartz raw material product becomes rough, and an uneven sandblasted surface is formed.

Further, when the blast-treated surface is formed, the stress generated in the cooling step after the ruthenium is processed is dispersed in a plurality of directions on the surface of the quartz to be blasted, thereby preventing the substance adhering to the surface of the quartz from proceeding. It is detached from the above surface upon cooling.

However, the quartz surface after the blasting treatment, on the other hand, causes the cerium particles to be detached from the wafer when the blasting surface is in contact with the wafer, or the particles are retained in the blasting surface of the product, and blasting is performed in the forming step of the quartz raw material product. The treatment is expanded in the surface region such that the particles float from the surface and fall onto the surface of the crystal on which the pattern is formed during the wafer processing process, thereby causing defects in the pattern.

The size of the above-mentioned particles to be produced is in the range of 0.2 μm to 5 μm, and even if the particle size is a small size of 0.3 μm or less, serious problems are caused, and in particular, it is required to be 0.18 μm or less in the fine semiconductor process. A wiring pattern, and it is important that the above-mentioned fine particles are not produced in such a fine semiconductor process, or the success rate (yield) can be reduced in the process of preparing a semiconductor wafer.

In other words, the quartz surface treatment by the conventional sand blasting process has a problem that the brittleness is high in the characteristics of the quartz raw material, and cracks can occur due to stress generated during the blasting treatment, and sparks, fine intervals and shapes can be generated on the surface. Complex quartz raw materials have a hindrance to the job. Moreover, when the first work is performed, only one product can be processed, and thus there is a problem that the operability and productivity are lowered, and it is difficult to apply to a large object.

Prior art literature

Accordingly, the present invention has been made to solve the above-mentioned problems, and the inventors of the present invention have provided continuous research and experimental results to provide a problem in the physical etching process caused by sand blasting in the process of processing the surface of a quartz raw material. And a surface treatment method, a surface treatment composition, and a composition for a quartz raw material which are easily and uniformly obtained by chemical processing of a quartz material tube and chemical etching of a plurality of parts to easily obtain a uniform and fine intaglio pattern. Made of quartz raw materials.

The problems to be solved by the present invention are not limited to the above-mentioned contents, and those skilled in the art to which the present invention pertains can easily understand other problems to be solved which are not mentioned.

According to an aspect of the present invention for achieving the above object, a surface treatment method for a quartz raw material for treating a surface of a quartz raw material, the surface treatment method for the quartz raw material, for the prepared quartz is provided a raw material preparation etching composition; an etching treatment step of etching the quartz raw material by the prepared etching composition; and a first cleaning step of cleaning the surface of the quartz raw material after performing the etching treatment step; a roughness adjustment step of adjusting a surface roughness of the quartz raw material after cleaning; a second cleaning step of cleaning the surface after performing the surface roughness adjustment step; and a drying step of ending the cleaning of the quartz The raw materials are dried.

In one aspect of the invention, preferably, the etching composition is composed of hydrofluoric acid (HF 50% solution), deionized water (18 MΩ or more), acidic ammonium fluoride (NH ₄ HF ₂ ), and formic acid. (HCOOH) is a mixture of the specified ratios.

In one aspect of the invention, preferably, the etching composition comprises 5 to 10% hydrofluoric acid (HF 50% solution), 5 to 10% deionized water (18 MΩ or more), and 20 to 40%. Acidic ammonium fluoride (NH ₄ HF ₂ ) and 50 to 70% formic acid (HCOOH).

In one aspect of the invention, preferably, the first cleaning step includes a step of cleaning with deionized water, and the surface roughness adjusting step includes using a buffered oxide etchant (BOE) diluent or hydrogen. Fluoric acid (HF) dilution to adjust The step of the entire surface roughness.

In one aspect of the invention, preferably, the first cleaning step and the second cleaning step are performed by using deionized water.

In one aspect of the invention, preferably, the surface-treated surface of the quartz material has a particle diameter of 10 μm to 100 μm, and preferably is adjusted in the surface roughness adjusting step. The average roughness of the surface is in the range of 0.5 to 2.0 μm.

In still another aspect of the present invention, a composition for surface etching treatment of a quartz raw material for etching a surface of a quartz raw material containing a hydrofluoric acid (HF 50% solution) is provided. ), deionized water (18 MΩ or more), acidic ammonium fluoride (NH ₄ HF ₂ ), and formic acid (HCOOH).

In still another aspect of the present invention, preferably, the composition for surface etching treatment of the quartz material comprises 5 to 10% of hydrofluoric acid (HF 50% solution) and 5 to 10% of deionized water (18 MΩ or more). 20-40% acidic ammonium fluoride (NH ₄ HF ₂ ) and 50-70% formic acid (HCOOH).

In another aspect of the present invention, a quartz raw material is provided, which is prepared by a surface treatment method of the above quartz raw material.

According to the surface treatment method of the quartz raw material, the surface treatment composition, and the quartz raw material produced thereby, it is possible to reliably exhibit a uniform and fine intaglio pattern on the surface of the quartz raw material, and it is possible to have a fine interval and a complicated shape. The raw materials are surface-treated, which has the effect of processing large materials and producing multiple parts.

The effects of the present invention are not limited to the above-described contents, and those skilled in the art to which the present invention pertains can easily understand other problems to be solved which are not mentioned.

S100‧‧‧Composition step for etching composition

S200‧‧‧ etching process steps

S300‧‧‧First cleaning step

S400‧‧‧ Surface roughness adjustment steps

S500‧‧‧Second cleaning step

S600‧‧‧ drying step

1 is a flow chart showing a surface treatment method of a quartz raw material of the present invention.

Figure 2 is an electron micrograph of the surface of quartz treated by the preparation method of the present invention (SEM) is a view showing the surface state of Example 2.

Other objects, features, and advantages of the present invention will become apparent from the description and appended claims.

Before the present invention is described in detail, it is to be understood that the invention may be All the changes, equivalent technical solutions, and alternative technical solutions included in the scope of the idea and the technical scope of the present invention are included.

When it is pointed out that a structural element is "connected" or "coupled" to another structural element, it is understood that it can be understood that it can be directly connected or coupled to another structural element, and it can also be understood that there are other structural elements in the middle. When it is pointed out that one structural element is "directly connected" or "directly connected" to another structural element, it should be understood that there are no other structural elements in the middle.

The terminology used in the description is for the purpose of describing particular embodiments, and is not intended to limit the invention. As long as there is no explicit meaning in the context, the singular representation includes the plural. It is to be understood that the terms "comprising" or "having" or "an" The existence or additional possibility of more than one other feature or number, step, action, structural element, component or combination thereof.

Further, terms such as "parts", "...units", "...modules" described in the specification may mean units for processing at least one function or action.

In the process of the description with reference to the drawings, the same reference numerals are given to the same components, and the repeated description thereof will be omitted. In the course of explaining the present invention, a detailed description of the related art will be omitted if it is not necessary to obscure the gist of the present invention.

Hereinafter, a surface treatment method of a quartz raw material according to a preferred embodiment of the present invention and a quartz raw material produced thereby will be described in detail with reference to the accompanying drawings.

First, the surface treatment method of the quartz raw material of the present invention is carried out with reference to FIG. Description. 1 is a flow chart showing a surface treatment method of a quartz raw material of the present invention.

As shown in FIG. 1, in the surface treatment method of the quartz raw material of the present invention, in the method of treating the surface of the quartz raw material (that is, embossing treatment), the surface treatment method of the quartz raw material includes: an etching preparation step S100, preparing an etching composition for the prepared quartz raw material; etching step S200, etching the quartz raw material by the prepared etching composition; first cleaning step S300, after performing the etching processing step, Cleaning the surface of the quartz raw material; the surface roughness adjusting step S400, adjusting the surface roughness of the cleaned quartz raw material; and the second cleaning step S500, after performing the surface roughness adjusting step, cleaning the surface And a drying step S600 of drying the quartz raw material that has been cleaned.

In the etching composition preparation step S100, the etching composition is defined by hydrofluoric acid (HF 50% solution), deionized water (18 MΩ or more), acidic ammonium fluoride (NH ₄ HF ₂ ), and formic acid (HCOOH). The ratio is mixed.

Preferably, the above etching composition is composed in the following ratio.

- Hydrofluoric acid (HF 50% solution): 5~10%

- Deionized water (18MΩ or more): 5~10%

- Acidic ammonium fluoride (NH ₄ HF ₂ ): 20 to 40%

-formic acid (HCOOH): 50~70%

Among them, in the case where the hydrofluoric acid is less than 5%, there is a problem that the etching phenomenon is lowered in the etching treatment step as a subsequent step, and in the case where the hydrofluoric acid is more than 10%, an overetching phenomenon occurs. Further, when the ammonium hydrogen fluoride is less than 20%, an unetched region is generated, and when the ammonium hydrogen fluoride is more than 40%, there is a problem that ammonium hydrogen fluoride cannot be dissolved and precipitated.

Further, when the formic acid is less than 50%, the intaglio form (embossed form) formed on the surface of the quartz raw material is increased to 100 μm or more, and when the formic acid is more than 70%, there is an intaglio form (embossed form). Reduce the problem to below 10μm. Among them, the size (particle diameter of the particles) formed in the surface of the quartz surface is preferably 10 μm to 100 μm, and more preferably 10 to 60 μm, so that it is suitable for use in the field of use of quartz raw materials.

At this time, in the process of preparing the composition for etching, glucose monohydrate may be contained in a predetermined ratio in order to adjust the viscosity.

The surface of the quartz raw material is etched by the etching composition prepared in this manner and by a chemical etching method (complete deposition or complete immersion) (step S200).

Then, after the etching treatment, the first cleaning step S300 is used to clean the surface of the quartz after the etching treatment, and therefore, it can be cleaned by using deionized water.

Next, the surface roughness adjusting step S400 for adjusting the surface roughness of the quartz material after cleaning is used to make the surface of the quartz material have a uniform roughness after etching, and therefore includes surface adjustment with a buffer etchant diluent. Or at least one of the surface roughness is adjusted with a HF (hydrofluoric acid) diluent.

Preferably, the quartz raw material subjected to the surface roughness adjusting step S400 is adjusted so that the average roughness Ra is in the range of 0.5 to 2.0 μm.

The second cleaning step S500 for cleaning the surface after the surface roughness adjustment step is for cleaning the diluent used in the surface roughness adjustment step, and therefore, is washed with deionized water.

Finally, the drying step S600 of drying the quartz raw material that has been washed is used to remove the residual moisture after the cleaning, and thus, drying is performed by, for example, dry air or a drying oven.

In such a process, the process time of each step can be adjusted in a variable manner by appropriately adjusting the surface roughness, and at normal temperature (for example, between 15 ° C and 20 ° C) and under atmospheric pressure in the atmosphere. get on.

The inventors of the present invention conducted experiments by the above surface treatment method.

Table 1 below is a table for sorting the results obtained by the surface treatment method of the present invention, and Table 2 is a table for finishing the results obtained in the comparative examples, which is a finishing process composition, working time and surface roughness. A table of relationships between.

Table 2

Fig. 2 is a view showing the surface state of Example 2 as an electron micrograph (SEM) of the surface of quartz treated by the production method of the present invention.

As described above, the surface treatment method of the quartz raw material of the present invention was confirmed by the present experiment, and it was possible to reliably exhibit a uniform and fine intaglio pattern on the surface of the quartz material, and to surface-treat the fine-section and the complicated material. It has the ability to process large quantities and produce multiple parts.

The embodiments and the drawings described in the specification are merely illustrative of a part of the technical idea of the invention. Therefore, the embodiments disclosed in the present specification are not intended to limit the technical idea of the present invention, but are used to explain the technical idea of the present invention. Therefore, the scope of the technical idea of the present invention is not limited to such an embodiment. It is to be understood that modifications and specific embodiments that can be easily deduced by those skilled in the art are within the scope of the invention as claimed in the appended claims.

S100‧‧‧Composition step for etching composition

S200‧‧‧ etching process steps

S300‧‧‧First cleaning step

S400‧‧‧ Surface roughness adjustment steps

S500‧‧‧Second cleaning step

S600‧‧‧ drying step

Claims (9)

A surface treatment method for a quartz raw material, comprising: an etching composition preparation step of preparing an etching composition for a prepared quartz raw material; and an etching treatment step of etching the quartz raw material by the prepared etching composition a first cleaning step of cleaning the surface of the quartz raw material after performing the above etching treatment step; a surface roughness adjusting step of adjusting the surface roughness of the quartz raw material after cleaning; and a second cleaning step After performing the surface roughness adjustment step, the surface is cleaned; and a drying step of drying the quartz raw material that has been cleaned, wherein the etching composition is hydrofluoric acid (HF 50% solution) Ionic water (18 MΩ or more), acidic ammonium fluoride (NH ₄ HF ₂ ), and formic acid (HCOOH) are mixed at a predetermined ratio. The surface treatment method for a quartz raw material according to claim 1, wherein the etching composition comprises 5 to 10% hydrofluoric acid (HF 50% solution), 5 to 10% deionized water (18 MΩ or more), 20~ 40% acidic ammonium fluoride (NH ₄ HF ₂ ) and 50-70% formic acid (HCOOH). The surface treatment method of the quartz raw material of claim 1, wherein the first cleaning step comprises the step of cleaning with deionized water, and the surface roughness adjusting step comprises diluting with a buffered oxide etchant (BOD). A step of adjusting the surface roughness with a liquid or hydrofluoric acid (HF) dilution. The surface treatment method of the quartz raw material of claim 3, wherein the first cleaning step and the second cleaning step are performed by using deionized water. The surface treatment method of the quartz raw material of claim 3, wherein the particle diameter of the surface-treated surface in the surface treatment method of the quartz raw material is 10 μm to 100 μm. The surface treatment method of the quartz raw material of claim 3, wherein the surface roughness is adjusted The average roughness of the surface obtained in the entire step was in the range of 0.5 to 2.0 μm. A composition for surface etching treatment of a quartz raw material comprising hydrofluoric acid (HF 50% solution), deionized water (18 MΩ or more), acidic ammonium fluoride (NH ₄ HF ₂ ), and formic acid (HCOOH). The composition for surface etching treatment of the quartz material according to claim 7, wherein the composition for surface etching treatment of the quartz material comprises 5 to 10% of hydrofluoric acid (HF 50% solution) and 5 to 10% of deionized material. Water (18 MΩ or more), 20-40% acidic ammonium fluoride (NH ₄ HF ₂ ) and 50-70% formic acid (HCOOH). A quartz raw material prepared by the surface treatment method of the quartz raw material according to any one of claims 1 to 6.