QUARTZ ETCHING METHOD AND ETCHED SUBSTRATE
20220048811 · 2022-02-17
Inventors
Cpc classification
C03C3/06
CHEMISTRY; METALLURGY
International classification
Abstract
A quartz etching method of the invention includes forming a mask on a quartz glass substrate and carrying out etching using a hydrofluoric acid-based etchant solution. The quartz etching method includes: preparing a quartz glass substrate; forming a mask having a predetermined pattern on the quartz glass substrate; and carrying out etching on the quartz glass substrate. When the quartz glass substrate is prepared, the quartz glass substrate is selected in accordance with a standard such that a concentration of hydroxyl groups included therein is less than or equal to 300 ppm.
Claims
1. A quartz etching method of forming a mask on a quartz glass substrate and carrying out etching using a hydrofluoric acid-based etchant solution, comprising: preparing a quartz glass substrate; forming a mask having a predetermined pattern on the quartz glass substrate; and carrying out etching on the quartz glass substrate, wherein when the quartz glass substrate is prepared, the quartz glass substrate is selected in accordance with a standard such that a concentration of hydroxyl groups included therein is less than or equal to 300 ppm.
2. The quartz etching method according to claim 1, wherein when the quartz glass substrate is prepared, the quartz glass substrate is selected in accordance with a standard such that birefringence thereof is less than or equal to 10 nm/cm.
3. The quartz etching method according to claim 1, wherein when the quartz glass substrate is prepared, the quartz glass substrate is selected in accordance with a standard such that the quartz glass substrate is formed of synthetic quartz produced by a vapor-phase axial deposition method.
4. The quartz etching method according to claim 1, wherein when the quartz glass substrate is prepared, the quartz glass substrate is selected in accordance with a standard such that the quartz glass substrate is stria free.
5. The quartz etching method according to claim 1, wherein when the mask is formed, the mask contains at least chromium as a main component.
6. The quartz etching method according to claim 1, wherein when the quartz glass substrate is etched, the quartz glass substrate is immersed in the hydrofluoric acid-based etchant solution.
7. An etched substrate produced by the quartz etching method according to claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0076] Hereinafter, a quartz etching method and an etched substrate according to a first embodiment of the invention will be described with reference to the drawings.
[0077]
[0078] The quartz etching method according to the embodiment is an etching method of forming a mask 11 on the quartz glass substrate 10 and carrying out etching using a hydrofluoric acid-based etchant solution (etchant).
[0079] As shown in
[0080] In the preparation step S01 shown in
[0081] Specifically, the quartz glass substrate 10 is selected in accordance with the standard such that the concentration of hydroxyl groups included therein is less than or equal to 300 ppm, preferably, less than or equal to 200 ppm and greater than or equal to 0 ppm.
[0082] At this time, the quartz glass substrate 10 is selected in accordance with the standard such that the birefringence thereof is less than or equal to 10 nm/cm and greater than or equal to 1 nm/cm. Furthermore, the quartz glass substrate 10 is selected in accordance with the standard such that the quartz glass substrate is formed of synthetic quartz produced by a vapor-phase axial deposition method. In addition, the quartz glass substrate 10 is selected in accordance with the standard such that the quartz glass substrate is stria free.
[0083] In the pretreatment step S02 of the quartz etching method according to the embodiment, as shown in
[0084] Here, the processing surface 10A of the quartz glass substrate 10 is polished using, for example, a polishing pad 50 and polishing liquid containing cerium oxide, preferably colloidal silica, as a main component. The number of polishing steps may be 0 times to multiple times which are freely selected. The quartz glass substrate 10 that was subjected to the polishing treatment is cleaned by a known cleaning method and thus the polishing liquid or the like adhered to the surface of the substrate is removed. Generally, as a method of cleaning of the quartz glass substrate 10, cleaning is carried out using a detergent, and then cleaning using deionized-water is carried out.
[0085] After the pretreatment step S02 is completed, the mask 11 having a predetermined pattern is formed on the quartz glass substrate 10 in the mask formation step S03 shown in
[0086] Here, there are a mask material film formation step and an etching mask formation step. In the mask material film formation step, a mask material film (mask) 11A that serves as an etching mask 11 is formed on the quartz glass substrate 10. In the etching mask formation step, a resist pattern 12 is formed on the mask material film 11A by patterning, the mask material film 11A is partially removed through the resist pattern 12 serving as a mask, and the etching mask 11 is thereby obtained.
[0087] In the mask material film formation step, as shown in
[0088] As a method of forming the chromium film serving as the mask material film 11A, it is preferable to use a sputtering method in consideration of mass productivity or the like. In this case, as a sputtering gas, it is preferable to use a mixed gas of argon gas, nitrogen gas, and carbon dioxide gas, and a flow ratio can be set so as to obtain a desired stress and reflectance. Particularly, a condition such as the flow rate of the nitrogen gas or the like is set such that the concentration of nitrogen included in the film is in the aforementioned range. Note that, as a sputtering apparatus, an apparatus including a known configuration can be used.
[0089] Here, film formation may be carried out such that the film composition of the mask material film 11A is adjusted to include nitrogen at greater than or equal to 15 atom % and less than 39 atom %. In the case of causing the mask material film 11A to contain nitrogen for adjusting the resistance of the mask material film 11A with respect to the etchant, it is preferable to form a film by a reactive sputtering method. In this case, when the mask material film 11A is formed, it is only necessary to add nitrogen into an inert gas such as argon or the like serving as a sputtering gas while using a target having a predetermined composition (chromium). Furthermore, oxygen such as various nitrogen oxides, various carbon oxides, or the like, nitrogen, a gas including carbon or the like may be adequately added. In addition, the concentration of nitrogen of the mask material film 11A is controlled by the proportion of the sputtering gas and sputtering power.
[0090] In the etching mask formation step, the resist pattern 12 is formed on the mask material film 11A by patterning, the mask material film 11A is partially removed through the resist pattern 12 serving as a mask, and the etching mask 11 is thereby obtained.
[0091] Here, firstly, resist is applied onto the mask material film 11A of the layered structure 30, the resist is subjected to treatment of exposure and development, and therefore the resist pattern 12 having openings 12a is formed as shown in
[0092] Next, as shown in
[0093] In the etching step S04 shown in
[0094] As an etching solution, for example, an etching solution including hydrofluoric acid (a hydrofluoric acid-based etching solution) can be used. The etching solution including hydrofluoric acid is not particularly limited. In the case in which the target processing speed is fast, the concentration of hydrofluoric acid can be set high. In the case in which the processing speed is slow, the concentration of hydrofluoric acid can be set low.
[0095] Etching of the quartz glass substrate 10 proceeds isotropically through the openings 11a of the etching mask 11 which are continuously connected to the openings 12a of the resist pattern 12. For this reason, as shown in
[0096] Specifically, in the wet etching treatment, the following etching apparatus is used.
[0097] The etching apparatus includes a substrate support unit, a reservoir, a swing unit, and a circulation unit.
[0098] In the etching apparatus, a plurality of the quartz glass substrates 10 are supported by the substrate support unit such that the plurality of quartz glass substrates 10 form one batch. Furthermore, the plurality of quartz glass substrates 10 and the substrate support unit are immersed in the etching solution stored in the reservoir.
[0099] At the same time, the swing unit supports the substrate support unit and can swing the substrate support unit. Moreover, the circulation unit can circulate the etching solution inside the reservoir in a state in which the quartz glass substrates 10 are immersed in the etching solution of the reservoir.
[0100] Accordingly, the etching apparatus carries out wet etching treatment such that, for example, five quartz glass substrates 10 form one batch.
[0101] After immersion in the etching solution is carried out for a predetermined amount of time, the plurality of quartz glass substrates and the substrate support unit are pulled up from the reservoir, and the etching solution is rinsed off the quartz glass substrates 10 by a rinsing unit.
[0102] As stated above, the amounts of etching at the etched portions corresponding to the plurality of openings 11a for each of the plurality of quartz glass substrates 10 are made uniform by swinging the quartz glass substrates 10 and circulating the etching solution.
[0103] Furthermore, new quartz glass substrates 10 are set to the substrate support unit in place of the processing-completed quartz glass substrates 10, and subsequent batch processing is carried out.
[0104] In the mask removal step S05, as shown in
[0105] In the embodiment, the recessed portions 10b are formed on the quartz glass substrate 10 by wet etching.
[0106] At this time, by preparing the quartz glass substrates 10 in accordance with the predetermined standard in the preparation step S01 as described above, the amounts of etching at the recessed portions 10b which are the etched portions can be equal to each other for one quartz glass substrate 10. Furthermore, the amounts of etching at the recessed portions 10b which are the etched portions can be equal to each other for the plurality of quartz glass substrates 10 of the same batch. Additionally, the amounts of etching at the recessed portions 10b which are the etched portions can be equal to each other for the plurality of quartz glass substrates 10 of each of various batches.
[0107] In the embodiment, it is necessary to note the following points.
[0108] At least in the case in which the etching rates are not uniform at the positions different from each other on one surface the quartz glass substrate 10, processing cannot be carried out such that all chips which are aligned on the quartz glass substrate 10 have the same shape.
[0109] For this reason, on one surface the quartz glass substrate 10, the etching rates at the positions different from each other need to be uniform.
[0110] Additionally, in the case of processing large quartz glass substrates having sizes of approximately six square inches which is described in the examples, the etching rate distribution of the quartz glass substrate needs to be uniform regardless of the positions of the quartz glass substrate.
[0111] For this reason, on one surface the quartz glass substrate 10, the etching rates at the positions different from each other need to be uniform.
[0112] Here, single wafer processing in which substrates are processed one by one while controlling each of the depths of the plurality of etched portions for each quartz glass substrate is known. According to the processing method, as long as the etching rate distribution is uniform on a surface of the quartz glass substrate, sufficient processing accuracy at each of the processing positions can be maintained. However, in this case, the productivity is inferior.
[0113] In contrast, the batch processing in which a plurality of quartz glass substrates is processed at the same time is advantageous in productivity as compared with the single wafer processing. However, in order to achieve the processing of a plurality of quartz glass substrates in the batch processing at the same time, it is necessary for the etching rates to be uniform at all of the etched portions of each of the quartz glass substrates to be processed at least in the same batch.
[0114] Consequently, the etching rates at all positions of the plurality of quartz glass substrates 10 to be processed in the same batch need to be uniform.
[0115] Furthermore, when the quartz glass substrates forming a batch, that is, the plurality of quartz glass substrates to be processed in the same batch, are selected, in the case in which substrates having etching rates different from each other are mixed, it is not possible to classify the substrates for each etching rate. For this reason, in the case in which substrates having etching rates different from each other are mixed, it is not possible to form a batch, that is, it is not possible to carry out batch processing.
[0116] Because of this, regarding the quartz glass substrates 10 to be processed in the same batch, it is necessary for the etching rates of all substrates to be the same as each other.
[0117] Furthermore, in the case in which etching rates are different from each other depending on a lot of the quartz glass substrates, it is necessary to classify the batch for each lot. In this case, it is difficult to classify the batch depending on the fractional number. Moreover, in this case, the time and effort for measuring an etching rate for each lot in advance increases.
[0118] Accordingly, regarding the quartz glass substrates 10 to be processed in the same batch, it is necessary for the etching rates of all lots to be the same as each other.
[0119] Note that the shape of the recessed portion 10b can be adequately selected.
EXAMPLES
[0120] Hereinafter, experimental examples of the quartz etching method according to examples of the invention will be described.
Experimental Examples 1 to 3
[0121] As a quartz glass substrate, a quartz glass substrate (vapor-phase axial deposition method, hydroxyl groups: 200 ppm or less, birefringence: 10 nm/cm or less) having a thickness of 1 mm and sizes of six square inches were used. Firstly, the quartz glass substrate was cleaned using detergent and deionized water, and thereafter a chromium film was formed under the following conditions using a DC sputtering method.
[0122] Sputtering gas: Ar/N.sub.2=86/8 (sccm)
[0123] DC power: 1.6 kW
[0124] As a result of AES analyzing at the film thickness of 150.0 nm of the formed chromium film, a gaseous component contained in the formed chromium film was 0/C/N=10/6/15 atom %.
[0125] Positive photosensitive resist was applied onto the formed chromium film by a spin coater to a film thickness of 1 μm. Next, the photosensitive resist was exposed and subjected to a development process, the chromium film was etched using a chromium etching solution containing Diammonium cerium nitrate as a main component, and thereafter an etching mask pattern on the quartz glass substrate was obtained.
[0126] Here, the etched portions of one quartz glass substrate were set at four points for each of the vertical and horizontal directions, that is, sixteen points as shown in
[0127] Note that the distance in vertical and horizontal directions between the etched portions was set to 40 mm. In addition, regarding the etched portions, the surface area of one point was set to 5 mm×5 mm.
[0128] Next, five quartz glass substrates per batch were set, and etching of the quartz glass substrates was carried out by the etching apparatus by immersing the quartz glass substrates in a glass etching solution containing hydrofluoric acid as a main component while swinging the quartz glass substrates and circulating the etching solution.
[0129] Additionally, the conditions of the etching treatment were set as follows.
[0130] Etchant solution; BHF
[0131] Therefore, the etching was carried out such that the depths of etching at the etched portions were 250 μm.
[0132] Furthermore, three batches were repeated, and the batches were each of experimental examples 1 to 3.
[0133] For the batch of each experimental example, the amounts of etching at the etched portions of each quartz glass substrate, that is, the depths of etching were measured. The results are shown in
[0134]
Experimental Example 4
[0135] As a quartz glass substrate, a quartz glass substrate (direct method, hydroxyl groups: 600 to 1300 ppm, birefringence: 30 nm/cm) having a thickness of 1 mm and a size of six square inches was used. In a similar manner to the above, the etching was carried out such that the depths of etching at the etched portions were 250 μm. This was experimental example 4.
[0136] Furthermore, the amounts of etching at the etched portions of the quartz glass substrate, that is, the depths of etching were measured. The results are shown in
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[0138] Additionally, variations 3σ% and 3σ μm in depth were calculated with respect to the depths of etching of the aforementioned experimental examples 1 to 4. The results are shown in Table 1.
TABLE-US-00001 TABLE 1 VARIATION EXPERIMENTAL EXPERIMENTAL EXPERIMENTAL EXPERIMENTAL INSIDE BATCH EXAMPLE 4 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 3 σ % 7.3% 0.45% 0.40% 0.73% 3 σ μm 18.1 μm 1.4 μm 1.2 μm 1.9 μm (CONVERSION OF 250 μm ETCHING)
[0139] As shown by the above results, the quartz glass substrates (direct method, hydroxyl groups: 600 to 1300 ppm, birefringence: 30 nm/cm) of experimental example 4 had the variations of 3σ=4% in depth on the surface of the substrate and 3σ=7% between the substrates. In contrast, in the quartz glass substrates (vapor-phase axial deposition method, hydroxyl groups: 200 ppm or less, birefringence: 10 nm/cm or less) of experimental examples 1 to 3, the variation in depth could be 3σ=1% or less in both the variation on the surface of the substrate and the variation between the substrates.
Experimental Examples 5 to 8
[0140] Next, for experimental examples 5 to 7, distribution of depth of etching on the surface of the fifth substrate of each batch of experimental examples 1 to 3 was measured. The results are shown in
[0141] Furthermore, for experimental example 8, distribution of depth of etching on the surface of the fifth substrate of the batch of experimental example 4 was measured. The results are shown in
[0142] In
[0143] From the above results, it is understood that the variations on the surface of the substrate in the cases of the quartz glass substrates (vapor-phase axial deposition method, hydroxyl groups: 200 ppm or less, birefringence: 10 nm/cm or less) of experimental examples 1 to 3 are smaller than in the case of the quartz glass substrates (direct method, hydroxyl groups: 600 to 1300 ppm, birefringence: 30 nm/cm) of experimental example 8.
[0144] Furthermore, with respect to the depths of etching of the aforementioned experimental examples 1 to 4, the variations 3σ% and 3σ μm in depth of experimental examples 5 to 8 were calculated. The results are shown in Table 2.
TABLE-US-00002 TABLE 2 VARIATION EXPERIMENTAL EXPERIMENTAL EXPERIMENTAL EXPERIMENTAL INSIDE BATCH EXAMPLE 4 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 3 σ % 4.0% 0.60% 0.36% 0.70% 3 σ μm 9.9 μm 1.5 μm 0.9 μm 1.7 μm (CONVERSION OF 250 μm ETCHING)
[0145] As shown by the above results, the quartz glass substrates (direct method, hydroxyl groups: 600 to 1300 ppm, birefringence: 30 nm/cm) of experimental example 8 had the variations of 3σ=4.0% in depth on the surface of the substrate. In contrast, regarding the quartz glass substrates (vapor-phase axial deposition method, hydroxyl groups: 200 ppm or less, birefringence: 10 nm/cm or less) of experimental examples 5 to 7, the variation in depth could be 3σ=0.7% or less on the surface of the substrate.
Experimental Examples 8 to 11
[0146] Furthermore, regarding the first and forth quartz glass substrates of the batch of the above-described experimental example 4, the distributions of depth of etching at the etched portions not only on the top surface side but also on the back surface side were measured in a manner similar to that described above, and these were experimental examples 9 to 11.
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[0149] Note that the horizontal axis shown in
[0150] Here, it is thought that, if the conditions of etching (etching apparatus) cause the variation in etching, the tendency of the variation in depth of etching varies on the top and the back of the quartz glass substrate, and there is no correlation therebetween.
[0151] However, as shown by the results in
[0152] Furthermore, the thickness of the quartz glass substrate of experimental example 4 is as thin as 1 mm, and it is thought that there is the same tendency regarding non-uniformity of the material on the top and the back of the quartz glass substrate.
[0153] Consequently, from the comparison of experimental examples 9 and 10, it is possible to consider that the variation in etching is caused by quartz (material).
INDUSTRIAL APPLICABILITY
[0154] Particularly, as the applicable examples of the invention, cases in which deep etching processing of approximately several hundreds of μm is necessary such as a component for MEMS, a component for a sensor, or the like are adopted. Moreover, as the applicable examples of the invention, processing of quartz glass substrates in which, even where tolerance is approximately ±several μm, the proportion % of the permitted tolerance with respect to the processing depth is small, and a strict value with respect to accuracy is demanded can be adopted.
[0155] The reason for this is that, for chemical reaction processing in which the processing of the entire processing area proceeds in a constant time such as etching, as compared with the case in which, for example, the required processing accuracy is approximately 10 μm±1 μm, a degree of accuracy is strict by one-digit in the case in which the required processing accuracy is approximately 100 μm±1 μm.
[0156] For machining processing, regarding the relationship of such dimensions, since both the cases are within the tolerance of ±1 μm, it is often regarded that there is no difference in the accuracy that is substantially required. In contrast, the case of etching treatment is different from the above-described situation.
[0157] Furthermore, the invention is also effective for the intended use because a required accuracy is small (strict) even in the case in which a required processing depth is shallow such as nanoimprint, or the like.
DESCRIPTION OF REFERENCE NUMERALS
[0158] 10 . . . quartz glass substrate [0159] 10a . . . recessed portion [0160] 11 . . . mask