KR20150080586A - Etching Method, Mask, Functional Component, and Method for Manufacturing Functional Component - Google Patents

Abstract

In the etching method, a mask including at least a film containing chromium and nitrogen is formed on a glass substrate, and etching is performed using a fluoric acid etching solution.

Description

(Etching method, mask, functional component, and method for manufacturing functional component)

The present invention relates to an etching method, a mask, a functional part, and a manufacturing method of a functional part, and more particularly, to a method of forming a fine uneven pattern or through hole on a glass substrate by etching and an etching mask used therefor, , A biochip, or the like, or an intermediate product.

The present application claims priority from Japanese Patent Application No. 2012-255742 filed on November 21, 2012, the contents of which are incorporated herein by reference.

In the field of MEMS (Micro Electro Mechanical Systems), fine pattern processing has been mainly performed on a silicon wafer. However, microscopic pattern processing on a glass substrate has been required, centering on bio relations represented by DNA (deoxyribonucleic acid) chips.

As a method of forming a desired concave portion by forming a mask on the glass substrate and etching to form a fine concave on the glass substrate, there is a method of forming a desired concave portion by forming a plurality of films A method of forming a mask and etching the concave portion has been proposed.

In addition, through holes for fixing biomolecules such as DNAs and proteins or cells having these biomolecules in the inside thereof in the thickness direction of the glass substrate or in a manufacturing process of a semiconductor device, In order to electrically connect, it is known to dispose an interposer between a semiconductor chip and a mounting substrate (see, for example, Patent Document 2). In this case, the interposer is provided with a through hole penetrating in the thickness direction, and a metal material is filled in the through hole or a metal film is formed on the inner face of the through hole to form a through contact, The substrate is electrically connected. In this case, in the above-described conventional example, a glass substrate is used as a substrate constituting the interposer.

As described above, the glass substrate is preferably used in order to cope with a specific use or miniaturization of a device. As a method of forming a through hole on a glass substrate, the following are known.

For example, a resist pattern is formed on one surface of a glass substrate, a protective film is formed on the other surface of the glass substrate, and a tapered through hole is formed by wet etching the glass substrate from the one surface over the resist pattern. Alternatively, a reduced tapered hole is formed from one surface of the glass substrate to an approximately intermediate position using a similar method, and then a reduced tapered hole is likewise formed from the other surface of the glass substrate to an approximately intermediate position. As described above, the through holes are formed through the holes formed from both sides of the glass substrate.

Chromium (Cr) is used as a metal mask material for wet etching by a fluoric acid etchant on a glass substrate (Patent Document 3).

<Prior Art Literature>

<Patent Literature>

Patent Document 1: Japanese Patent Application Publication No. 3788800

Patent Document 2: JP-A-2010-70415

Patent Document 2: JP-A-2008-307648

However, when a chromium film is used for wet etching with a fluoric acid etching solution on a glass substrate, the chromium film can withstand the etching solution sufficiently in a short time etching such as a shallow groove, but as in the case of forming a deep groove, When the etching is performed for a long time, the chrome film is corroded by the fluoric acid etchant and the resistance is deteriorated to cause pinholes. In the worst case, the chrome film is completely dissolved. Further, when a fine pinhole of the chromium film causes defects on the surface of the glass substrate, damage to the chromium film due to corrosion even in a short time of etching may cause defects due to pinholes.

Therefore, conventionally, as in Patent Document 1, measures have been taken such as forming a film by depositing a metal having excellent corrosion resistance on a chromium film with gold or the like. However, in this method, the noble metal such as gold is expensive, the number of times of film formation increases, and etching of the mask film suited to the kind of metal is required, complicating the process. As a result, the number of working steps is increased, and the working time is increased and the cost is raised, and there has been a demand for improvement.

In addition, when using a mask with a plurality of layers for the etching for a long time, 500 to the glass substrate having a large surface area of 5000 cm ² or so, if a large number to form a hole of approximately the depth 50 ㎛, the inner surface of the glass substrate direction There is a problem in that an unbalance such as a depth dimension and a diameter dimension of each hole is generated. This problem is considered to be related to the nonuniformity of the supply of the etchant in the inside of the hole due to the fact that the thickness of the mask composed of a plurality of layers becomes as large as several mu m to several ten mu m. This problem also occurs in the process of forming a through hole and the process of forming a hole not penetrating, and there has been a demand to solve this problem.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described circumstances, and it is an object of the present invention to provide an etching solution which is simple in structure, improved in resistance to an etchant, can be reduced in thickness, A mask, a functional part, and a method of manufacturing a functional part by providing a mask capable of performing processing for a long period of time and capable of maintaining the in-plane uniformity capable of improving the yield.

An etching method according to the first aspect of the present invention is characterized in that a mask including at least a film containing chromium (Cr) and nitrogen (N) is formed on a glass substrate and etching is performed using a fluoric acid etchant do.

In the etching method according to the first aspect of the present invention, the mask includes chromium as a main component, and the mask may contain nitrogen of 15 atomic% or more and less than 39 atomic%.

In the etching method according to the first aspect of the present invention, the film exhibits a broad halo pattern in X-ray diffraction and may not have a diffraction peak.

In the etching method according to the first aspect of the present invention, the depth of the recess formed in the glass substrate by the etching may be set to 10 to 500 탆.

In the etching method according to the first aspect of the present invention, the average thickness of the mask may be 5 to 500 nm.

The mask according to the second aspect of the present invention includes a film disposed between the etching liquid and the glass substrate and containing at least chromium (Cr) and nitrogen (N) in etching using a hydrofluoric acid etching liquid.

The mask according to the second aspect of the present invention may contain chromium as a main component and may include nitrogen of 15 atom% to less than 39 atom%.

A functional component according to a third aspect of the present invention includes: a glass substrate; And a film containing at least chromium (Cr) and nitrogen (N) formed on the glass substrate.

In order to exhibit stable performance in terms of mass production, in the functional component according to the third aspect of the present invention, the film may contain chromium as a main component and may contain nitrogen of 15 atom% to less than 39 atom% have.

According to a fourth aspect of the present invention, there is provided a method of manufacturing a functional component, comprising: forming a mask including at least a film containing chromium (Cr) and nitrogen (N) on a glass substrate; And etching is performed to form a hole or a concave portion having a depth of 10 to 500 占 퐉 on the glass substrate.

In the method for manufacturing a functional component according to the fourth aspect of the present invention, a mask containing chromium as a main component and containing a film containing nitrogen (N) in an amount of 15 atomic% or more and less than 39 atomic% can be formed on a glass substrate have.

According to the etching method of the first aspect of the present invention, it is possible to optimize the composition ratio of nitrogen contained in the chromium film by including a film containing nitrogen of 15 atomic% or more and less than 39 atomic% to improve the resistance of the chromium film to the fluoric acid etching solution It is possible to wet etch the glass with less generation of pinholes without using a noble metal such as gold. Therefore, with the mask of the chrome single layer containing nitrogen, it is possible to have a sufficient etching solution resistance even with the film thickness not affecting the supply of the etching liquid into the hole in the process, and also to the large- Can be maintained.

Here, when the content of nitrogen contained in the mask deviates from the above range (15 atomic% or more to less than 39 atomic%), the resistance to the etching solution deteriorates and pinholes (pits) It is not preferable.

In the etching method according to the first aspect of the present invention, a wet etching process is applied to a glass substrate having a micro concavo-convex structure or a through hole formed on the surface thereof, and a laminate including the etching mask of the wet etching process stacked on the surface of the glass substrate In the structure, it is possible to form a laminated structure containing chromium in a main component of the etching mask (mask) and containing nitrogen of 15 atomic% or more and less than 39 atomic%.

In the etching method according to the first aspect of the present invention, the mask may contain nitrogen of 15 atomic% or more and less than 39 atomic%. Further, the mask may contain nitrogen of 15 atomic% or more and 37 atomic% or less.

In the etching method according to the first aspect of the present invention, it is preferable that the mask has a plurality of layers including a layer other than the film containing nitrogen in which the main component is chromium at 15 atomic% or more and less than 39 atomic% have. At this time, the mask may have a layer made of a dissimilar metal other than chromium or a material which becomes a resistance.

Further, the mask may have a plurality of layers composed of a chromium film. At this time, the plurality of layers constituted by the chromium film may be composed of the adhesion layer, the main layer and the antireflection layer, and the main layer may be a film containing nitrogen in which the main component is chromium at 15 atomic% or more and less than 39 atomic%.

In the etching method according to the first aspect of the present invention, means for setting the depth of the concave portion formed in the glass to 10 to 500 mu m or means for setting the average thickness of the mask to 5 to 500 nm may be adopted . The etching method according to the first aspect of the present invention can prevent the occurrence of pinholes and improve the resistance to the etching solution even in the processing of the surface width condition or the processing depth condition that can not guarantee uniformity in the in- It is possible to maintain the accuracy of the process dimension by maintaining the process until the end time of the process.

In addition, in the etching method according to the first aspect of the present invention, the film included in the mask can contain a very small amount of carbon and a very small amount of oxygen in addition to nitrogen, and in the case of the hydrofluoric acid, It is possible.

Further, in the etching method according to the first aspect of the present invention, the mask has the etching resistance described above by including a film having a broad halo pattern in X-ray diffraction and having a main component chromium which does not have a sharp diffraction peak.

The mask according to the second aspect of the present invention is characterized in that, for etching using a hydrofluoric acid etching solution, chromium is disposed as a main component between the etching solution and the glass substrate, and at least 15 atomic% and less than 39 atomic% . &Lt; / RTI &gt;

A functional component according to a third aspect of the present invention comprises: a glass substrate; The film may include a film formed on the glass substrate and containing at least chromium as a main component and containing nitrogen of 15 atomic% or more and less than 39 atomic%, and may have necessary etching solution resistance.

A method of manufacturing a functional component according to a fourth aspect of the present invention is a method for manufacturing a functional component, comprising: forming a mask on a glass substrate including at least a film containing chromium as a main component and containing nitrogen at 15 atomic% or more and less than 39 atomic% Etching is performed on the surface of the glass substrate using a fluoric acid etching solution to form holes or concave portions having a depth of 10 to 500 占 퐉 so as to prevent the accuracy of process dimensions and the occurrence of pinholes.

According to the respective aspects of the present invention, the composition ratio of nitrogen contained in the chromium film is optimized to improve the resistance of the chromium film to the hydrofluoric acid etchant, and even when a noble metal such as gold is not used, Wet etching can be obtained.

1A is a cross-sectional process diagram showing an etching method according to the first embodiment of the present invention;
1B is a cross-sectional process diagram showing an etching method according to the first embodiment of the present invention;
1C is a cross-sectional process diagram showing an etching method according to the first embodiment of the present invention;
1D is a cross-sectional process diagram showing an etching method according to the first embodiment of the present invention;
1E is a cross-sectional process diagram showing an etching method according to the first embodiment of the present invention;
1F is a cross-sectional process diagram showing an etching method according to the first embodiment of the present invention;
2A is a cross-sectional process diagram showing a second embodiment of an etching method according to the present invention;
2B is a cross-sectional process diagram showing an etching method according to a second embodiment of the present invention;
2C is a cross-sectional process diagram showing an etching method according to a second embodiment of the present invention;
3 is a plan view showing the surface of the glass substrate in the etching method according to the third embodiment of the present invention;
4 is a photograph showing an experimental example of an etching method according to the present invention;
5 is a graph showing XRD in an experimental example of an etching method according to the present invention;
6 is a graph showing diffraction peaks of XRD, Cr, and CrN in an experimental example of an etching method according to the present invention.

A first embodiment of an etching method according to the present invention will be described below with reference to the drawings.

1A to 1F are cross-sectional process drawings showing an etching method in the present embodiment, and reference numeral 10 denotes a glass substrate.

In the etching method according to the present embodiment, the pretreatment step of polishing the surface 10A of the glass substrate 10 on which the fine concavo-convex structure is formed and cleaning the polished glass substrate 10, A step of forming a resist pattern 12 on the mask material film 11A by patterning and forming a resist pattern 12 as a mask on the mask material film 11A; And a wet etching process using the resist pattern 12 and the etching mask 11 as a mask to remove the mask material film 11A from the glass substrate 11 10, and a removal step of removing the etching mask 11 on the glass substrate 10. The etching process of FIG.

1A, the surface 10A of the glass substrate 10 on which the fine concavo-convex structure is formed is polished, and the glass substrate 10 after polishing is cleaned do.

The constituent material of the glass substrate 10 prepared in this preprocessing step is not particularly limited. (E.g., Neoceram), quartz glass, lead glass, potassium glass, borosilicate glass (Tempax Float made by Schott), synthetic quartz glass, (Additive) other than SiO ₂ from a glass close to pure SiO ₂ , such as soda lime glass, aluminosilicate glass, low-temperature anodic bonding glass (SW series manufactured by Asahi Glass Co., Ltd.) Glass, and so on.

1A, the work surface 10A of the glass substrate 10 is polished by using, for example, a polishing pad 50 and a polishing liquid containing cerium oxide as a main component. This polishing process can be carried out arbitrarily several times at zero times. The glass substrate 10 after the polishing treatment is cleaned using a known cleaning method, and the polishing liquid adhering to the surface of the substrate is removed. As a cleaning method for the glass substrate 10, it is general to perform cleaning using a detergent and then pure cleaning.

In the mask material film forming step, a mask material film (mask) 11A to be an etching mask 11 is formed on the glass substrate 10 as shown in Fig. 1B. Thus, the laminated structure 30 is formed as the glass substrate 10 and the mask material film 11A.

The mask material film 11A contains, as a main layer, a film containing chromium as a main component and nitrogen of 15 atomic% or more and less than 39 atomic%. The average thickness of the chromium film of the mask material film 11A can be set to 5 to 500 nm, for example, 100 to 300 nm.

In the method of forming the chromium film as the mask material film 11A, it is preferable to use the sputtering method in consideration of mass productivity and the like. In this case, it is preferable to use a mixed gas of argon gas, nitrogen gas and carbon dioxide gas as the sputtering gas, and the flow rate ratio can be set so as to obtain desired stress and reflectance. Particularly, a condition such as a nitrogen gas flow rate is set so that the nitrogen concentration in the film is in the above range (15 atomic% or more to less than 39 atomic%). As the sputtering apparatus, a device having a known structure can be used. A detailed description of the film forming conditions and device configuration will be given later.

In the etching mask forming step, a resist pattern 12 is patterned on the mask material film 11A and the mask material film 11A is partially removed through the resist pattern 12 as a mask to remove the etching mask 11 .

Here, first, a resist is applied to the mask material film 11A of the laminated structure 30, exposed and developed to form a resist pattern 12 having an opening 12a as shown in Fig. 1C . 1D, the mask material film 11A is partially removed by a wet etching process using the resist pattern 12 as a mask so as to form openings (not shown) through the openings 12a of the resist patterns 12 11a are formed in the mask material film 11A. Thereby, an etching mask 11 having a planar pattern of a predetermined shape is obtained.

In the glass etching step, using the etching mask 11 and the resist pattern 12 formed on the glass substrate 10 as a mask, a wet etching process using an etching solution of hydrofluoric acid is performed. As the etching solution, for example, an etching solution containing hydrofluoric acid (hydrofluoric acid etching solution) may be used. The etching solution containing hydrofluoric acid is not particularly limited, but it is possible to increase the hydrofluoric acid concentration when the desired processing speed is high and to lower the hydrofluoric acid concentration when the processing speed is slow.

In this wet etching process, the etching of the glass substrate 10 is progressed isotropically from the opening 11a of the etching mask 11 continuous to the opening 12a of the resist pattern 12, , And a semicircular concave portion 10b is formed at a position corresponding to the opening 11a. It is general to use a fluoric acid etchant for etching the glass substrate 10. As the fluoric acid-based etching solution, a mixed solution of hydrofluoric acid, hydrofluoric acid and inorganic acid, or ammonium fluoride to hydrofluoric acid may be used.

In the removing step, as shown in Fig. 1F, when the etching mask 11 and the resist pattern 12 on the glass substrate 10 are peeled off using a known peeling method, A glass substrate on which the concave portion 10b is formed can be obtained. Such a glass substrate can be used as a specific functional part (for example, MEMS, DNA chip, etc.).

Here, the film composition of the mask material film 11A is adjusted so as to contain nitrogen of 15 atom% or more and less than 39 atom% of chromium as the main component to form a film. Since it is necessary to contain nitrogen in the mask material film 11A in order to adjust the etching solution resistance of the mask material film 11A, it is preferable to perform the deposition by the reactive sputtering method. In this case, in order to deposit the mask material film 11A, nitrogen may be added to an inert gas such as argon as a sputtering gas using a target of a predetermined composition (chrome). In addition, a gas containing oxygen, nitrogen, carbon or the like such as various kinds of nitrogen oxides and various kinds of carbon oxides may be appropriately added. The nitrogen concentration of the mask material film 11A is adjusted by controlling the sputtering gas ratio and the power of the sputtering.

Further, in the present embodiment, the mask material film 11A is a film which shows a wide halo pattern in X-ray diffraction and does not have a diffraction peak.

By containing nitrogen in chromium, it is possible to generally increase the hydrofluoric acid performance.

Further, when chromium is sputtered in a nitrogen-containing atmosphere, by controlling the nitrogen content, it is possible to obtain a state in which there is no diffraction peak (amorphous state) by showing a wide halo pattern in X-ray diffraction. By making this state, since the grain boundaries can be eliminated, there is no permeation of liquid from the crystal grain boundaries, and the hydrofluoric acid performance can be further improved. The amorphous chromium film containing nitrogen exhibits the above-mentioned performance, and has sufficient hydrofluoric acid performance even if it contains trace amounts of carbon and oxygen.

According to the present embodiment, the glass substrate 10 on which the fine concavo-convex structure (concave portion 10b) is formed on the surface 10A to be processed by the wet etching process and the surface 10A to be processed of the glass substrate 10 The mask material film 11A is composed of a single layer film of chromium added with nitrogen in the laminated structure 30 having the mask material film 11A in which the etching mask 11 of the wet etching process is formed in a stacked manner .

With this configuration, pinholes can not be generated in the mask material film 11A (etching mask 11) even when the wet etching proceeds, when the concave portion 10b is formed in the glass substrate 10 by wet etching . Therefore, a desired concave portion 10b can be formed without a defective portion such as a lack in the edge portion of the concave portion 10b formed on the surface 10A of the glass substrate 10 to be processed. Namely, since the mask material film 11A (etching mask 11) of the nitrogen-containing chromium mono-layer film can be formed on the glass substrate 10, the structure can be simplified. In addition, since the concave portion 10b can be surely formed on the work surface 10A of the glass substrate 10, the yield can be improved.

Further, the mask material film 11A (etching mask 11) was formed of a nitride film containing chromium as a main component.

As described above, the adhesion of the mask material film 11A to the glass substrate 10 can be enhanced by using chromium as a main component. Furthermore, by making the mask material film 11A a nitride film, the etching solution resistance can be improved, and the opening 11a corresponding to the concave portion 10b can be easily formed. Therefore, it is possible to reliably form the concave portion 10b on the surface 10A of the glass substrate 10 without forming a defect due to the pin hole, thereby improving the yield.

In addition, wet etching treatment was carried out while leaving the resist pattern 12 formed on the etching mask 11.

This configuration makes it possible to prevent the occurrence of defects in the concave portion 10b of the glass substrate 10 resulting from a defect such as a pinhole or a pinhole in the etching mask 11, .

In the present embodiment, the mask material film 11A is made of a nitrogen-containing chromium mono-layer film, but it is also possible to use any one of an oxide film, a nitride film or a carbide film containing chromium as a main component, Lt; / RTI &gt; In addition, an oxide film, a nitride film, or an oxynitride film containing as a main component a metal or an alloy such as Ni, Mo, Ti, Al, Cu, Au, or Pt may be laminated as the additional laminated film. Particularly, in order to set the reflectance to a desired range, an oxide film can be laminated.

In the present embodiment, it has been found that the addition of nitrogen gas is effective in improving the resistance of a chromium film to a hydrofluoric acid etching solution, and the composition ratio of nitrogen contained in the chromium film is optimized. This makes it possible to wet etch the glass with less occurrence of pinholes, even if a noble metal such as gold is not used. As the material to be treated, it is possible to apply a material which does not have a flat surface shape like a substrate.

Hereinafter, a second embodiment of an etching method according to the present invention will be described with reference to the drawings.

2A to 2C are cross-sectional process drawings showing an etching method in the present embodiment, and reference numeral 10 denotes a glass substrate.

In the etching method according to the present embodiment, a case where a glass substrate is formed with a top surface, a metal mask is formed on the top surface of the glass substrate, and the glass substrate is wet-etched from the top surface of the glass substrate to form a through- Explain.

The etching method according to the present embodiment also includes a pretreatment step, a mask material film formation step, an etching mask formation step, a glass etching step and a removal step, similarly to the first embodiment.

In the etching method of the present embodiment, chromium films (mask material films) 11 and 13 containing nitrogen in the same range as in the first embodiment are formed to have a thickness of 100 to 300 nm, for example, Are formed on the upper surface 10A and the lower surface 10B, respectively (mask material film forming step). The material of the glass substrate 10 is the same as that of the first embodiment. As the film forming method of the chromium films 11 and 13, it is preferable to use the sputtering method as in the first embodiment.

However, the deposition rate of the chromium film 13 by the sputtering method is not so high, and if the thickness of the chromium film 13 is increased, the productivity is lowered. Taking this point into consideration, the thickness of the chrome film 13 is set within the above range.

Then, a resist pattern 12 is formed on the surface of the chrome film 11 (mask material film forming step). The resist is applied, for example, to a thickness of 1 to 3 占 퐉 by a spin coating method. A resist pattern 12 is formed by exposing a pattern for forming a through hole to the resist thus coated and developing it with a developer. Then, the chromium film 11 is wet etched and patterned over the resist pattern 12 to form a chromium mask 11 (etching mask forming step) as shown in FIG. 2A. As the etching liquid for the chromium film 11, for example, an etching solution containing cerium nitrate ammonium can be used, and an acid such as nitric acid or perchloric acid can be added.

Next, as shown in FIG. 2B, the glass substrate 10 is wet-etched over the chromium mask 11 (glass etching step). As the etching solution, a fluoric acid etching solution can be used. Further, a mixed solution of diluted hydrofluoric acid, buffered hydrofluoric acid (BHF), and inorganic acid may be used in accordance with the material of the glass substrate 10 and a desired etching rate. When wet etching is performed for a predetermined time, a through hole 10c penetrating in the thickness direction of the glass substrate 10 is formed as shown in Fig. 2C. By controlling the etching time, it is possible to control the diameter d of the through hole 10c on the glass substrate surface 10B. For example, when a rigid glass substrate 10 such as borosilicate glass is etched, a through hole 10c having a depth of 100 占 퐉 is formed under the condition of a processing speed of 0.3 占 퐉 / min and a processing time of 5 hours. Alternatively, when a soft glass substrate such as soda glass is etched, a through hole 10c having a depth of 300 占 퐉 is formed under the condition of a processing speed of 1 占 퐉 / min and a processing time of 5 hours. When the through hole 10c is formed, the chromium film 13 is exposed at the lower portion.

At this time, since the nitrogen-containing chromium film 13 has a good adhesion to the glass substrate 10, the etching solution hardly penetrates between the exposed chromium film 13 and the glass substrate 10, The lower surface 10B of the substrate 10 is not etched in its plane direction (lateral direction in the drawing). The through hole 10c has a circumferential wall portion 10d having a tapered shape tapering from the upper surface 10A to the lower surface 10B of the glass substrate 10 so that the line constituting the circumferential wall portion 10d has an inflection point Without doing so, it reaches (10B). That is, it is possible to prevent protrusions from being formed in the middle of the cross section of the through hole 10c of the glass substrate 10. [

Thereafter, the resist pattern 12 is peeled off, and the chromium mask 11 and the chromium film 13 are dissolved in the etching solution and removed (a removing step). From this, it is possible to manufacture the glass substrate 10 on which the through hole 10c is formed. As the resist stripping solution, a known alkaline resist stripping solution can be used. As the etching solution, the above-mentioned cerium nitrate ammonium can be used.

When the pore d of the through hole 10c in the glass substrate 10B is set to be, for example, 3 mm or more, the etching of the glass substrate 10 proceeds and the bottom of the through hole 10c is exposed The chromium film 13 is peeled from the glass substrate surface 10B and a clearance is formed and the glass substrate surface 10B is etched in the surface direction as the etchant is impregnated into the gap to form a protrusion on the peripheral wall of the through hole 10c It is also possible to provide a protective member (protective film) for protecting the chromium film 13 under the glass substrate 10 prior to the wet etching of the glass substrate 10.

In this case, the protective member may be a film such as the resist 12 or an adhesive protective film made of resin.

Also in this embodiment, the same effect as that of the first embodiment can be obtained. Further, in the process of forming a structure having a deeper processing depth than that of the through hole 10c, that is, in a process with a longer processing time, the etching solution resistance is further required. In this case, however, It becomes possible.

Furthermore, the present invention is not limited to the above embodiment. For example, in the case where the metal films 11 and 13 include a nitrogen-containing chromium film having good etching resistance, a film having high adhesion to the glass substrate 10 or a laminated film obtained by laminating at least two kinds of metal films Lt; / RTI &gt; For example, a laminated film of a single film selected from a Cr film, a Si film, and a Ni film and an Au film, or a laminated film of a Cr film, an Ni film, and an Au film can be used. The glass substrate 10 on which the through hole 10c is formed can also be used for a biochip, an interposer, or other applications.

Hereinafter, a third embodiment of the etching method according to the present invention will be described with reference to the drawings.

Fig. 3 is a front view showing a glass substrate according to the present embodiment. In Fig. 3, reference numeral 10 denotes a glass substrate.

In the present embodiment, only the size of the glass substrate 10 and the position of the concave portion 10c to be formed differ from the first and second embodiments described above. And a description thereof will be omitted.

In this embodiment, the glass substrate 10 has a surface size of at least 1500 cm ² , for example, 370 mm 470 mm. On the surface 10A, a glass substrate 10 having a depth of 50 탆 and a diameter of 10 탆 A plurality of concave portions 10c are provided. The distance between adjacent recesses 10c is about 1 mm.

The mask 11 of the present embodiment is the same mask as the first and second embodiments.

In the present embodiment, the thickness of the mask 11 is made thinner so that the variation in the depth dimension can be made within 1% even in the formation of the concave portion 10c in which the etching liquid needs to be intruded to process the inside thereof.

Particularly, in the case of forming a large number of holes having a depth dimension of about 50 to 500 times the mask thickness dimension on a glass substrate having a large area of about 500 to 5000 cm ² in a long time etching, It is possible to prevent an imbalance such as a depth dimension and a diameter dimension of each hole from being generated.

Hereinafter, embodiments of the present invention will be described.

<Experimental Example 1>

As the glass substrate, borosilicate glass (Tenpax: manufactured by Schott) was used. After cleaning the glass substrate with detergent and pure water, a chromium film was formed by DC sputtering under the following conditions.

Sputtering gas: Ar / N ₂ = 86 (sccm) / 8 (sccm) CD power: 1.6 kW

The thickness of the formed chromium film was 150.0 nm. As a result of the analysis by AES, the contained gas component was O / C / N = 10 atomic% / 6 atomic% / 15 atomic%.

A positive type photosensitive resist was coated on the chromium film formed with a thickness of 1 탆 by a spin coater. Subsequently, the photosensitive resist was exposed and developed, and the chromium film was etched with an etching solution for chromium mainly containing cerium nitrate ammonium, thereby obtaining a mask pattern for glass etching. The glass substrate was immersed in a glass etching solution containing fluoric acid as a main component and its surface was observed every hour, and the surface after immersion for 5 hours was observed.

The results are shown in Table 1 and Fig. 4, Photo 1.

Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 The deposition gas (sccm) Ar 86 71 80 61 N ₂ 8 34 0 51 Power kW 1.6 1.6 1.6 1.7 Thickness (A) 1500 1500 1500 1500 Film composition (atom%) O 10 8 20 8 C 6 7 2 8 N 15 37 2 39 Immersion time Etching rate 0.3 탆 / min 1 hours O O △ O 2 hours O O X O 3 hours O O X △ 4 hours O O X X

O: No pinhole occurred

Δ: Partial occurrence of pinholes

X: Multiple pinholes or full occurrences

From this result, it can be seen that pits (pinholes) do not occur even after 5 hours, and the chromium film as the glass etching mask film exhibits high resistance to the inner glass etching solution.

<Experimental Example 2>

As the glass substrate, borosilicate glass (Tenpax: manufactured by Schott) was used. Similarly, after the substrate was cleaned, a chromium film was formed under the following conditions using DC sputtering.

Sputtering gas: Ar / N ₂ = 71 (sccm) / 34 (sccm) CD power: 1.6 kW

The thickness of the formed chromium film was 150.0 nm. As a result of the analysis by AES, the gas component contained was O / C / N = 8 atomic% / 7 atomic% / 37 atomic%. On the formed chromium film, a positive photosensitive resist was coated with a thickness of 1 mu m by a spin coater. Subsequently, the photosensitive resist was exposed and developed, and the chromium film was etched with an etching solution for chromium mainly containing cerium nitrate ammonium, thereby obtaining a mask pattern for glass etching. The substrate was immersed in a glass etching solution containing fluoric acid as a main component, the surface of the substrate was observed every hour, and the surface after immersion for 5 hours was observed.

The results are shown in Table 1 and Fig. 4, Photo 2.

From this result, it can be seen that pits (pinholes) do not occur even after 5 hours, and the chromium film as the glass etching mask film exhibits high resistance to the inner glass etching solution.

<Experimental Example 3>

As the glass substrate, borosilicate glass (Tenpax: manufactured by Schott) was used. Similarly, after the substrate was cleaned, a chromium film was formed under the following conditions using DC sputtering.

Sputtering gas: Ar / N ₂ = 80 (sccm) / 0 (sccm) CD power: 1.6 kW

The thickness of the formed chromium film was 150.0 nm. As a result of the analysis by AES, the contained gas component was O / C / N = 20 atomic% / 2 atomic% / 2 atomic%. On the formed chromium film, a positive photosensitive resist was coated with a thickness of 1 mu m by a spin coater. Subsequently, the photosensitive resist was exposed and developed, and the chromium film was etched with an etching solution for chromium mainly containing cerium nitrate ammonium, thereby obtaining a mask pattern for glass etching. The substrate was immersed in a glass etching solution containing fluoric acid as a main component and its surface was observed every hour, and the surface after immersion for 5 hours was observed.

The results are shown in Table 1 and Photo 3 in Fig.

From this result, a pit (pinhole) was generated in an elapsed time of one hour, and the function as a mask was lost in a state where 2 hours had elapsed. Further, after 5 hours, the chromium film itself is almost peeled off. This chromium film is remarkably corroded by the glass etching solution, and the resistance of the glass etching solution is very low.

<Experimental Example 4>

As the glass substrate, borosilicate glass (Tenpax: manufactured by Schott) was used. Likewise, after the substrate was cleaned, a chromium film was formed under the following conditions by DC sputtering.

Sputtering gas: Ar / N ₂ = 61 (sccm) / 51 (sccm) CD power: 1. 7 kW

The thickness of the formed chromium film was 150.0 nm. As a result of the analysis by AES, the contained gas component was O / C / N = 8 atomic% / 8 atomic% / 39 atomic%. On the formed chromium film, a positive photosensitive resist was coated with a thickness of 1 mu m by a spin coater. Subsequently, the photosensitive resist was exposed and developed, and the chromium film was etched with an etching solution for chromium mainly containing cerium nitrate ammonium, thereby obtaining a mask pattern for glass etching. The substrate was immersed in a glass etching solution containing fluoric acid as a main component, the surface of the substrate was observed every hour, and the surface after immersion for 5 hours was observed.

The results are shown in Table 1 and Fig. 4, Photo 4.

From this result, it can be seen that pit (pinhole) did not occur after 2 hours but pits were generated in the state of 3 hours passed, and the chromium film was corroded to generate a large number of pinholes, .

From the above results, it can be seen that the etching solution resistance of the sputtering film containing nitrogen in the range of 15 atomic% or more and less than 39 atomic% of chromium as the main component of the present invention is very preferable in the etching treatment of the glass substrate.

From the above results, it can be seen that the ratio in which O / C is included does not affect the etchant resistance of the chromium film.

In the above Experimental Examples 1 to 4, X-ray diffraction (XRD) with 2? In the range of 20 to 80 占 was carried out, and the results are shown in Figs. 5 and 6. Fig. In addition, in FIG. 5, the intensities of Experimental Examples 1 to 4 are indicated by being easily pushed apart, but they are almost the same intensity range except for the peak.

From this result, in the case where the main component of the present invention is a chromium film, a halo pattern in XRD was confirmed in a film in which pinholes did not occur in Experimental Examples 1 and 2, that is, in a nitrogen range with high HF resistance. On the other hand, peaks were observed in the films in which the pinholes of Experimental Examples 3 and 4, that is, other than the durability nitrogen range (15 atomic% or more and less than 39 atomic%) as described below.

In particular, peaks of (1, 1, 0) planes of Cr were observed at less than the lower limit of nitrogen (15 atomic%) shown in Experimental Example 3, , 1, 0), and (0, 1, 1) are overlapped with each other. Peaks of (1, 1, 0) planes of Cr and (1, 1, 0) and (0, 1, 1) planes of CrN are shown below in Experimental Examples 1 to 4 as Fig.

Further, as a result of the XRD of the chrome film containing nitrogen having high HF resistance of the present invention, since a wide halo pattern is observed at a low angle side and does not have a diffraction peak, the present inventor has found that the chromium film is amorphous amorphous). Of course, when strictly defined, XRD alone is difficult, but it is judged that the chromium film is sufficiently amorphous because it does not show a peak based on Cr or CrN crystals.

10: glass substrate
10A: Surface
10b: concave portion (micro concavo-convex structure)
10c: Through hole
11, 13: etching mask
11A: mask material film
12: Resist pattern (resist film)
30: laminated structure

Claims (11)

A method for forming a mask, comprising: forming a mask including at least a film containing chromium (Cr) and nitrogen (N) on a glass substrate; and performing etching using a hydrofluoric acid etchant. The etching method according to claim 1, wherein the mask contains chromium (Cr) as a main component and nitrogen of 15 atom% to less than 39 atom%. The etching method according to claim 1 or 2, wherein the film exhibits a broad halo pattern in X-ray diffraction and does not have a diffraction peak. The etching method according to claim 1 or 2, wherein the depth of the concave portion formed on the glass substrate by the etching is set to 10 to 500 탆. 4. The etching method according to any one of claims 1 to 3, wherein the average thickness of the mask is 5 to 500 nm. And a film containing at least chromium (Cr) and nitrogen (N), disposed between the etchant and the glass substrate in etching using a fluoric acid etching solution. The mask according to claim 6, comprising chromium (Cr) as a main component and nitrogen (N) not less than 15 atomic% and not more than 39 atomic%. A glass substrate; And
A film formed on the glass substrate and containing at least chromium (Cr) and nitrogen (N);
. The functional component according to claim 8, wherein the film contains chromium (Cr) as a main component and nitrogen (N) of 15 atomic% or more and less than 39 atomic%. A mask including at least a film containing chromium (Cr) and nitrogen (N) is formed on a glass substrate,
Etching is performed on the surface of the glass substrate using a fluoric acid etching solution,
A hole or concave having a depth of 10 to 500 占 퐉 is formed on the glass substrate. A functional part according to claim 10, characterized in that a mask including chromium (Cr) as a main component and a film containing nitrogen (N) of 15 atomic% or more and less than 39 atomic% is formed on a glass substrate &Lt; / RTI &gt;

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