JP2001010070A - Etching method for processing a substrate, dry etching method for polyetheramide resin layer, manufacturing method of inkjet recording head, inkjet head and inkjet printing apparatus - Google Patents

Abstract

(57) Abstract: An etching method that can use a mask material that does not cause defects such as pinholes and can perform highly reliable etching, and inkjet recording using the method. To provide a head manufacturing method, an inkjet head, and an inkjet printing apparatus. An etching method for processing a substrate by etching, comprising: an etching method using a polyetheramide resin layer as an etching resistant mask; and a dry etching method for a polyetheramide resin layer, the method comprising: A dry etching method for etching an etheramide resin layer with an etching gas containing oxygen as a main component is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching method for processing a substrate and a dry etching method for a polyether amide resin layer, and more particularly to a method for forming an ink supply port of an ink jet head and a pressure sensor. The present invention relates to a Si anisotropic etching method used for machining technology, or a dry etching method suitable for etching a protective film as an ink-resistant layer of an ink jet head or a protective film of a semiconductor device.

[0002]

2. Description of the Related Art As an etching method used for micromachining, a chemical etching technique using a photolithography technique is mainly used. Here, as a substrate to be used, a silicon (Si) substrate (wafer) having a crystal orientation of <100> and <110> planes is generally used. By performing alkali-based chemical etching on the Si substrate having the above plane orientation,
The etching direction can be selected in the depth (digging) direction and the width (spreading) direction, thereby obtaining anisotropic etching. For example, it is possible to form a hole having a large depth and a small width. Also, <10
When a substrate having a crystal orientation of 0> plane is used, the depth direction can be controlled since the depth direction is geometrically determined by the width to be etched. For example, it is possible to obtain a hole that becomes narrower at an inclination of 54.7 ° in the depth direction from the etching start surface. Therefore, by considering the thickness of the substrate and the width to be etched, it is possible to reliably and easily control the formation of holes halfway through the substrate without penetrating the substrate (see FIG. 4). It is well known that the above-described properties of etching are applied to micromachining technology such as manufacturing of an ink jet head and manufacturing of a pressure sensor.

[0003]

By the way, chemical etching using an alkaline etching solution is generally performed with a strong alkali for a long period of time, and furthermore, heat treatment is performed during this period. , to use a dielectric film such as SiO _2, SiN film is generally used. However, these films are usually sputtered or CV
Since these films are formed as deposited films such as D, it is difficult to form these films without defects, and the heads and the like sometimes become defective due to the defective portions (pinholes).
In addition, there is a situation in which processing becomes finer year by year, and as a result, minute defects cannot be ignored. As described above, in micromachining technology such as head manufacturing, formation of a defect-free etching mask is becoming a great demand.

Accordingly, the present invention solves the above-mentioned problems, and can use a mask material which has alkali resistance and does not cause defects such as pinholes, thereby performing highly reliable etching. It is an object of the present invention to provide a simple etching method, a method of manufacturing an ink jet recording head using the method, an ink jet head and an ink jet printing apparatus.

[0005]

SUMMARY OF THE INVENTION In order to achieve the above objects, the present invention provides an etching method for processing a substrate, a dry etching method for a polyetheramide resin layer, a method for manufacturing an ink jet recording head, An ink jet head and an ink jet printing apparatus are configured as follows. That is, the etching method of the present invention is an etching method in which an etching resistant mask having a desired opening pattern is provided on a substrate to perform processing of the substrate, and etching is performed through the etching resistant mask. It is characterized in that a polyetheramide resin layer is used as an etching mask. Further, in the etching method of the present invention, the etching resistant mask has a two-layer structure of a polyetheramide resin layer and a dielectric layer, and the polyetheramide resin layer is provided on the dielectric layer. It is characterized by. Further, the etching method of the present invention,
The opening of the polyetheramide resin layer as the etching resistant mask is formed by dry etching with an etching gas containing oxygen as a main component. Further, in the etching method of the present invention, the opening of the polyetheramide resin layer as the etching resistant mask is formed by dry etching with an etching gas mainly containing a mixed gas of oxygen and carbon tetrafluoride. It is characterized by: The etching method according to the present invention is characterized in that a silicon wafer is used as the substrate. Further, the etching method of the present invention is characterized in that the etching is anisotropic etching. Further, a dry etching method of the present invention is a dry etching method for a polyetheramide resin layer, wherein the polyetheramide resin layer is etched by an etching gas containing oxygen as a main component. Further, the dry etching method of the present invention is a dry etching method for a polyether amide resin layer, wherein the polyether amide resin layer is etched with an etching gas mainly containing a mixed gas of oxygen and carbon tetrafluoride. It is characterized by: In the dry etching method according to the present invention, the dry etching uses a silicon-containing photoresist as an etching mask for the dry etching. Further, in the dry etching method of the present invention, in the dry etching method of embedding a plurality of processed objects in the same by plasma excitation using microwave discharge, the plurality of processed objects are etched using the above dry etching method. It is characterized by doing.

[0006] A method of manufacturing an ink jet head according to the present invention is a method of manufacturing an ink jet head for discharging ink, in which a substrate constituting the ink jet head is prepared, and a polyetheramide resin layer is formed on the surface of the substrate. Forming a mask pattern made of and then performing an etching process using the mask pattern as a mask. Further, the method of manufacturing an ink jet head of the present invention is a method of manufacturing an ink jet head for discharging ink, in which a substrate constituting the ink jet head is prepared, and a polyether is formed on a dielectric layer on the surface of the substrate. The method is characterized by comprising a step of forming a mask pattern composed of a layer having a two-layer structure in which an amide resin layer is formed, and performing an etching process using the mask pattern as a mask. In the method of manufacturing an ink jet head according to the present invention, the mask pattern is formed by dry etching using an etching gas containing oxygen as a main component. Also,
The method of manufacturing an ink jet head according to the present invention is characterized in that the mask pattern is formed by dry etching using an etching gas mainly containing a mixed gas of oxygen and carbon tetrafluoride. Further, a method of manufacturing an ink jet head according to the present invention is characterized in that an ink supply port penetrating the substrate is formed by the etching. Further, a method of manufacturing an ink jet head according to the present invention is characterized in that a silicon wafer is used as the substrate. In the method for manufacturing an ink jet head according to the present invention, an electrothermal conversion element and an ink flow path member used for discharging ink are formed on the substrate. Further, in the method for manufacturing an ink jet head according to the present invention, the etching is anisotropic etching. Further, in the method for manufacturing an ink jet head of the present invention, a substrate constituting an ink jet head is prepared, and a protective film as an ink-resistant layer made of a polyetheramide resin layer is formed on the surface of the substrate. It is characterized by processing by any of the dry etching methods of the present invention. Further, in the method of manufacturing an ink jet head according to the present invention, the protective film is a protective film formed on the substrate including at least a heat acting portion, and the opening of the heat acting portion is processed by etching the protective film. It is characterized by doing.

[0007] Further, the ink jet head of the present invention comprises:
A substrate constituting an inkjet head is prepared, a mask pattern made of a polyetheramide resin layer is formed on the surface of the substrate, and etching is performed using the mask pattern as a mask. It is characterized by that. In addition, the ink jet head of the present invention prepares a substrate constituting the ink jet head, and forms a mask pattern consisting of a two-layer structure in which a polyetheramide resin layer is formed on a dielectric layer on the surface of the substrate. And performing an etching process using the mask pattern as a mask. Further, an inkjet head according to the present invention is characterized in that the mask pattern is formed by any one of the above-described dry etching methods according to the present invention. Further, the inkjet head according to the present invention is characterized in that an ink supply port penetrating the substrate is formed by the etching. Further, the inkjet head according to the present invention is characterized in that a silicon wafer is used as the substrate. Further, the inkjet head according to the present invention is characterized in that the substrate is provided with an electrothermal conversion element and an ink flow path member used for discharging ink. Further, the inkjet head of the present invention,
The etching is anisotropic etching. Further, in the ink jet head of the present invention, a substrate constituting the ink jet head is prepared, and a protective film as an ink resistant layer made of a polyetheramide resin layer is formed on the surface of the substrate. Characterized by being processed by any one of the dry etching methods. Further, the inkjet head of the present invention is characterized in that the protective film is a protective film formed at least on a heater portion of the head substrate, and the opening of the heater portion is processed by etching the protective film. . Further, an ink jet printing apparatus of the present invention is an ink jet printing apparatus for performing printing by discharging ink, wherein an ink jet head for discharging ink is constituted by any one of the above ink jet heads of the present invention. It is characterized by:

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the configuration of the present invention described above,
The polyether amide resin used in the present invention has high strength, flexibility, high resilience to external stress, and excellent chemical resistance, and is not affected by acids, alkalis, aromatic solvents, and the like. It is excellent in heat resistance and moisture resistance, it can be dissolved in a polar solvent to form a varnish, and it is a material that can be formed at a relatively low temperature just to remove the solvent. By using a polyetheramide resin layer as a mask when etching a constituent substrate, defects such as pinholes generated in the mask at the time of forming the mask can be reduced. Also,
In the present invention, by using a mask having a two-layer structure in which a polyetheramide resin layer is formed on a dielectric layer as the mask, in addition to being able to reduce the above-described defects, it is possible to improve the precision in, for example, anisotropic etching. An etching process can be performed.

Further, since the polyether amide resin itself is not photosensitive, patterning thereof is generally performed by using a dispenser or by screen printing. Therefore, the polyether amide resin can be used for applications such as a moisture-proof coating agent for electronic components, which do not require fine patterning, but fine patterning is required. It has been difficult to use it as an etching mask in a micromachining technique or the like, or a protective film as an ink-resistant layer of an ink jet recording head.
Because, in order to perform fine patterning on the polyetheramide resin, it is necessary to cover the polyetheramide resin with an etching mask and dissolve unnecessary parts with a solvent. This is because there was no suitable masking material to withstand. However, according to the method for dry-etching the polyetheramide resin layer of the present invention, fine patterning is possible, and therefore, such a protective film as an ink-resistant layer of an ink jet recording head that requires such fine patterning is also used. It can be used.

[0010]

Embodiments of the present invention will be described below with reference to the drawings. [Embodiment 1] (a) to (d) are diagrams showing a configuration of an ink jet head according to Embodiment 1 of the present invention, and (b)
1A is a cross-sectional view taken along the line AA ′ of FIG. 1A, FIG. 1C is a schematic plan view of the Si substrate part, and FIG. 1D is a schematic cross-sectional view of the Si substrate part. 1A and 1B, the ink jet head includes a discharge port plate 5 having discharge ports 6 corresponding to the electrothermal transducers 5 and a Si substrate for supplying ink from the back surface of the Si substrate 1. 1 has a configuration having an ink supply port 4 opened therein, and has a configuration of a side shooter type ink jet head for discharging ink substantially perpendicularly to a substrate surface.

In FIG. 1 (c), an electrothermal transducer for generating thermal energy used for ink ejection shown in FIGS. 1 (a) and 1 (b) is provided on one substrate surface 1A of the substrate 1. A member for forming the ink flow path is formed. In addition, an ink supply port 4 is formed in the center of the substrate 1 as a penetrating hole, so that ink can be supplied from the back surface of the substrate 1 to the ink flow path on the front surface 1A side. Note that, in the figure, reference numeral 3 indicates a polyetheramide resin layer for a mask pattern formed in the following manufacturing process.

FIGS. 2A to 2C are schematic views showing a part of the manufacturing process of the ink jet head according to this embodiment. First, as shown in FIG.
Using the i-substrate 1, a polyetheramide resin layer 3 is formed on the etching start surface 1B side by spin coating. In one embodiment of the present invention, thermoplastic polyetheramide (trade name: HL-1200, manufactured by Hitachi Chemical Co., Ltd.) is used as the polyetheramide resin layer 3. The above-mentioned thermoplastic polyetheramide is commercially available as a solution dissolved in a solvent, and after forming this into a desired film thickness by spin coating, the solvent component is removed by heating and drying, so that the thermoplastic polyetheramide resin is removed. Layer 3 can be formed. Here, regarding the setting of the film thickness to be applied, in view of obtaining a defect-free etching mask which is the object of the present invention, since there is a correlation between the film thickness and the defect occurrence rate, an experiment by the present inventors has 2 μm in thickness
It has been confirmed that the above is effective.

Next, as shown in FIG. 2 (b), a pattern of an etching mask is formed by the thermoplastic polyetheramide resin layer 3. This pattern is formed as follows. When the thermoplastic polyetheramide used in the present embodiment is used as the material of the resin film 3, since no photosensitive component is added to this material, first, in order to form a thermoplastic polyetheramide pattern, A resist pattern (not shown) is separately formed by photolithography using a photoresist. Then, using the resist pattern, the thermoplastic polyetheramide is etched to form an etching mask shown in FIG. In this case, the etching of the thermoplastic polyetheramide is dimethylformamide, dimethylsulfoxide,
This can be performed using a solvent such as N-methylpyrrolidone. However, the above-mentioned photoresist, which is a mask material at the time of dissolution and removal, requires solvent resistance. For this reason, in this embodiment, in consideration of the solvent resistance to the above-mentioned solvent, a dry etching method using a reaction gas without using this solvent is used.
As this reaction gas, RIE (reactive ion etching) using O ₂ gas or plasma ashing can be used.

In the dry etching using this reaction gas, the photoresist used as a mask and the thermoplastic polyetheramide are etched at substantially the same rate. No problem occurs when the thickness is twice or more the thickness of the film. After etching the thermoplastic polyetheramide 3 into a predetermined pattern, the photoresist is peeled off, and FIG.
The state shown in (b) can be obtained.

Next, as shown in FIG. 2C, a supply port 4 is formed by anisotropic etching using the thermoplastic polyetheramide resin film 3 as a mask. In the anisotropic etching, KOH and NaO which are alkaline etching liquids are used.
H, TMAH or the like can be used. However, since there is a correlation between the concentration of the solution, the processing temperature, the etching rate, and the smoothness of the etched surface, in this embodiment, TM
AH22wt% was etched at a processing temperature of 80 ° C. The etching rate in this case is about 30 to 40 μm / h
Becomes If the etching solution comes into contact with the surface of the substrate 1 on the side opposite to the etching start surface during the etching, a problem may arise if the above-mentioned thermoplastic polyetheramide is applied to the entire surface or protected. It is possible to use a tool or the like to take measures to prevent the etching solution from touching.

The thermoplastic polyetheramide as the resin film 3 used as the etching mask after the completion of the anisotropic etching is removed if necessary. As a removing means, a solvent or a dry etching method can be used as in the method used for forming the pattern of the thermoplastic polyetheramide described above. As described above, by using the thermoplastic polyetheramide resin film 3 as an etching resistant mask for anisotropic etching, an inkjet head can be formed at a relatively low cost and easily. 2A to 2C, a known process can be used for the process after the manufacturing process of the ink jet head, whereby the ink jet head can be completed, but the description is omitted. I do. The head according to the present embodiment is of a so-called side shooter type that discharges ink in a direction perpendicular to the substrate 1.

Embodiment 2 Embodiment 2 of the present invention
An object of the present invention is to provide a configuration that is more effective in reducing defects in the etching mask. That is, FIG.
As shown in (c), an etching mask is formed with a two-layer structure of the dielectric layer 2 and the polyetheramide resin layer 3. Originally, as an etching resistant mask for anisotropic etching,
Although the dielectric film 2 is reliable and generally used, it is relatively difficult to form the dielectric 2 over the entire surface of the Si substrate 1 without defects as described above. For this reason, in this embodiment, a two-layer structure is used as described above.

As shown in FIG. 3A, SiO ₂ or SiN is formed on the entire surface of the Si substrate 1 as the dielectric film 2, and the polyether amide resin layer 3 is formed thereon similarly to the first embodiment. To form A necessary pattern is formed in the same manner as in Example 1 using thermoplastic polyetheramide as the polyetheramide resin layer 3. Then, using this pattern as a mask, the dielectric film 2 is etched. As a means for etching the dielectric film 2, a known method using a mixed solution of hydrofluoric acid and ammonium fluoride or a dry etching method using a reaction gas can be used.

In this embodiment, the pattern of the thermoplastic polyetheramide is used as an etching mask for both the etching of the dielectric film and the anisotropic etching. It is also possible to set the pattern formation of the polyetheramide in a separate step. Such a case is effective when there is a concern that the thermoplastic polyetheramide may be damaged by the etchant used for the dielectric film. As mentioned above,
With the structure of the dielectric film which is advantageous for the adhesiveness of the Si substrate and the anisotropic etching solution and the organic resin which compensates for the defect of the dielectric film, it is possible to provide an etching method with good pattern accuracy and yield.

FIG. 5 is a schematic perspective view showing an ink jet printing apparatus which can use the ink jet head obtained by this embodiment. In the inkjet printing apparatus 100, the carriage 101 is slidably engaged with two guide shafts 104 and 105 extending parallel to each other. Thereby, the carriage 101
Can be moved along the guide shafts 104 and 105 by a driving motor and a driving force transmission mechanism such as a belt for transmitting the driving force (both are not shown). An ink jet unit 103 having an ink jet head and an ink tank as an ink container for storing ink used in the head is provided on the carriage 101.
Is mounted.

The ink jet unit 103 includes a head for discharging ink and a tank as a container for storing ink supplied to the head. That is, each of the four colors of black (Bk), cyan (C), magenta (M), and yellow (Y) is ejected.
The heads and tanks provided corresponding to each of these heads are mounted on the carriage 101 as the ink jet unit 103. The respective heads and the tank are detachable from each other, and are provided so that only the tank can be replaced for each ink color as needed when the ink in the tank runs out. Of course, only the head can be replaced as needed. The configuration of attaching and detaching the head and the tank is not limited to the above example,
It goes without saying that the head and the tank may be integrally formed.

The paper 106 serving as a print medium is inserted from an insertion port 111 provided at the front end of the apparatus, and finally its transport direction is reversed, and is transported by a feed roller 109 to a lower portion of the moving area of the carriage 101. You. As a result, printing is performed from a head mounted on the carriage 101 to a print area on the sheet 106 supported by the platen 108 as the head 101 moves.

As described above, printing on the entire sheet 106 is performed while alternately repeating the printing of the width corresponding to the width of the ejection opening arrangement of the head and the feeding of the sheet 106 in accordance with the movement of the carriage 101. Is discharged to the front of the device. At the left end of the movable area of the carriage 101, a recovery system unit 110 that can oppose each head on the carriage 101 and a lower part thereof is provided.
This makes it possible to perform operations such as capping the ejection openings of each head and suctioning ink from the ejection openings of each head during non-printing or the like. The predetermined position at the left end is set as the home position of the head. On the other hand, at the right end of the device, an operation unit 1 having switches and display elements is provided.
07 is provided. The switches here are used for turning on / off the power of the apparatus, setting various print modes, and the like, and the display element plays a role of displaying various states of the apparatus.

[Embodiment 3] Hereinafter, further preferred embodiments to which the dry etching method for polyetheramide resin of the present invention is applied will be described. The polyether amide resin is used as a protective film as an ink-resistant layer of the inkjet head, for example, as shown in FIG. When an opening is formed in a layer by etching, if there is a residue due to etching on the cavitation-resistant layer forming the heat acting portion, foaming becomes unstable or a discharge amount fluctuates, and ink jet recording is performed. The ejection performance of the head is adversely affected. In particular, in recent ink jet recording heads aiming at improvement of print quality by flying fine liquid, even minute residues which have not been a problem in the past can not be ignored.

In the above-described dry etching method,
The etching rate is small and the throughput is not so high. However, if the substrate temperature is increased to increase the etching rate, the resist is deteriorated by the heat of the increased substrate temperature, and there is a problem in that the resist cannot be removed with a general stripping solution. In particular, in the case of such dry etching, a thin film-like residue that cannot be removed even by etching or a removing liquid is generated on the etched surface, so that fine processing is required, and further improvement in print quality is required. As a desired etching method for a protective layer of an ink jet head, it has not been suitable for adopting as it is. On the other hand, according to the dry etching method of the polyether amide resin of the present embodiment, that is, the dry etching method of etching with an etching gas containing a mixed gas of oxygen and carbon tetrafluoride as a main component, the temperature rise of the substrate is suppressed. 1000Å / m in the case of conventional oxygen plasma without generating etching residues
The etching rate as small as around "in" can be greatly improved.

Next, a third embodiment in which such a polyether amide resin is subjected to a dry etching method will be described in detail. In Example 3, first, as a polyether amide, HIMAL HL-1200 (manufactured by Hitachi Chemical Co., Ltd.) was applied by a spinner, pre-dried at 90 ° C. for 30 minutes, and further dried at 250 ° C. to obtain a sample. The etching rate of the etching was determined. The measurement of the film thickness was performed with an optical film thickness meter.

FIGS. 6 to 9 show the measurement results of the etching rate. 6 to 8 show the RF frequency of 2.46 GHz.
FIG. 6 shows the relationship between the gas composition and the etching rate, FIG. 7 shows the relationship between the pressure and the etching rate, and FIG. 8 shows the relationship between the RF output and the etching rate. FIG. 9 shows the RF frequency 1
This shows the relationship between the gas composition and the etching rate when using an anode coupling type etching apparatus at 3.56 MHz. By adding CF _4,
It can be seen that the etching rate is remarkably improved.

With respect to the gas composition, the addition amount of CF ₄ can be arbitrarily changed, but it is preferable to add 2% or more with respect to the O ₂ flow rate from the viewpoint of rate and residue. Regarding the direction in which the amount of CF ₄ is increased, the base may be etched at the time of over-etching. It is necessary to select the gas composition. In addition, when CF ₄ is excessively added, the etching rate is conversely lower than that when no CF ₄ is added. Therefore, the flow rate of oxygen is preferably set to 30% or less. In particular, the range of 5% to 15% is preferable. As for the gas pressure, a stable condition is selected according to the characteristics of the apparatus. Generally, from 10Pa to 30
It is performed in the range of 0 Pa. Regarding gas flow rate and RF power, appropriate conditions are selected according to the characteristics of the apparatus. In addition,
It goes without saying that an inert gas such as nitrogen can be added to oxygen or carbon tetrafluoride as an etching gas in order to stabilize the plasma or improve the etching rate.

Next, patterning was performed using the resist as a mask, and the patterning characteristics were evaluated. First, HIMAL HL is placed on a silicon wafer (6 inches).
-1200 was applied by a spinner at 2 µm, dried under the above conditions, and then patterned using OFPR-800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a resist. The thickness of the resist was 5 μm. As an etching condition, an etching apparatus having an RF frequency of 2.46 GHz was used, and O ₂ 1000 sc was used as an etching gas.
cm, the CF ₄ 100 sccm, pressure 50 Pa,
Etching was performed at an RF power of 500 W. The same sample was used, and the RF frequency was 13.56 MHz.
Etching was performed with an etching apparatus of 0.8 W / cm ² , using O ₂ 100 sccm as an etching gas and CF _{4 10} sccm at a pressure of 50 Pa and a stage temperature of 50 ° C.

As a result, no etching residue was generated, the patterning was well cut, and the resist could be peeled off without any problem. The maximum temperature of the substrate at this time is 90
℃, 80 ℃. The stripping of the resist is performed using a stripper 111
2A (manufactured by Shipley) was performed at room temperature while applying ultrasonic waves. As for the accuracy of patterning, a good result was obtained with a finish of -2 μm with respect to the width of the resist pattern, and a variation of about ± 10%.

[Embodiment 4] Conventionally, a novolak positive photoresist has been used as a dry etching mask from the viewpoints of dry etching resistance and fine workability. Although the etching selectivity of the polyamide resin is not sufficient in terms of the etching selectivity (an etching rate similar to that of the polyamide resin), since the conventional photolitho line can be used as it is, the above-described method is performed by increasing the film thickness. The disadvantages have been addressed. For example, in the case of etching a 2 μm polyamide, a novolak-based positive resist having a film thickness of about 5 to 8 μm has been used. Therefore, the exposure and development time of the photoresist is long, and there is a problem in productivity. On the other hand, according to the silicon-containing photoresist etching mask of the embodiment, an ink jet recording head of high productivity and high quality fine droplets is produced with either the side shooter type or the edge shooter type. It becomes possible.

In the method for dry etching a polyether amide resin according to the present invention, the means using a silicon-containing photoresist as an etching mask may be a dry etching using a plasma excitation method by a microwave discharge of a batch type (a plurality of sheets). By applying the present invention to an apparatus, the productivity of patterning can be remarkably improved as compared with a conventional apparatus. Conventionally, it is known that when the same processing is performed on a plurality of workpieces by the above-described dry etching apparatus, there is a loading effect in which the etching rate changes depending on the number of processed workpieces (processing area). Also, when performing patterning of polyetheramide resin, the peak of the etching rate is shifted due to the effect of such loading, and the etching area is not more than 5 inch wafer.
Almost no loading effect. Such a tendency is similarly observed in the case where the polyetheramide resin is dry-etched with a mixed gas of oxygen and carbon tetrafluoride. FIG. 10 shows a polyetheramide resin (HIMAL HL-12 manufactured by Hitachi Chemical Co., Ltd.) on a 5-inch wafer.
00) is a result of measuring the etching rate using a batch dry etching apparatus CDE-7-4 (microwave power supply) manufactured by Shibaura Seisakusho. The etching was performed for 1 minute, and the film thickness was measured by an optical method. The etching condition is such that the total flow rate of CF ₄ and O ₂ is 900
It was fixed to sccm, and the amount of CF ₄ added was changed. power,
The pressure is fixed at 700 W and 50 Pa. Wafer loading (processing amount per batch) was changed to 0.5 W (wafer), 1 W, 3 W, and 5 W. As is apparent from FIG. 10, the peak has a peak at a certain composition. On the left side of the peak, carbon tetrafluoride is insufficient and the rate becomes small. On the contrary, on the right side of the peak, the supply of carbon tetrafluoride becomes excessive and the rate becomes low. Goes down. That is, the peak position differs depending on the number of processed sheets. Therefore, when etching a polyether amide resin using a batch-type etching apparatus, a dummy having substantially the same form as that of a processed object is put in, and the number of processed wafers is adjusted. It is necessary to deal with it at different times. However, in the method for dry etching a polyether amide resin of the present invention, the means using a silicon-containing photoresist as an etching mask is applied to a dry etching apparatus using a plasma excitation method by microwave discharge of a batch type (multiple processing). By doing so, it is possible to realize the patterning of the polyetheramide resin at a high throughput without taking the above-mentioned means for reducing the productivity.

Hereinafter, the fourth embodiment will be described in more detail. In Example 4, as a polyether amide,
HIMAL HL-1200 (manufactured by Hitachi Chemical Co., Ltd.) was applied at 2 μm using a spinner, preliminarily dried at 90 ° C. for 30 minutes, and further dried at 250 ° C. On top of that, as a Si-containing resist, for example, FH-SP (trade name) manufactured by Fuji Hunt Electronics Technology Co., Ltd. was applied with a 1 μm spinner and patterned under the following conditions. Pre-bake oven 90 ° C x 20 minutes Exposure PLA-600F (manufactured by Canon) 400mj / cm ² Development Positive resist developing solution NMD-3 manufactured by Tokyo Ohka Room temperature dip 25 seconds Rinse Pure water 1 minute Drying rinser dryer Si-containing resist is alkali as a polymer. It is composed of a soluble silicone polymer and a naphthoquinonediazide-based photosensitive material. The Si content of the base polymer is about 20%. Basically, Si-containing photoresist can be processed as it is in a normal novolak-based positive resist line, and no new equipment is required.

In a conventional novolak-based positive resist, the etching rate is about the same as that of the polyether amide resin, so that the film thickness is 5 to 8 μm. Therefore, the exposure time was long and the development time was long, and there was a problem in productivity. S
By using the i-containing resist, the etching resistance is dramatically improved, and the coating film thickness can be reduced to about 1 μm. Therefore, the exposure time is reduced to 1/4 and the development time is reduced to 1/5, and the productivity of patterning is significantly improved. Improved.

Next, etching was performed with a dry etching apparatus CDE-7-4 using microwaves manufactured by Shibaura Seisakusho Co., Ltd. The etching conditions are as follows. Gas CF ₄ / O ₂ = 85 sccm / 815 sccm Etching pressure 50 Pa Power 700 W (2.45 GHz) Time 2 min (Loading 5 5 inch wafers, etching area is 5 inch wafer × 0.3) The film loss after etching is 0. This is a level of about 1 μm, which is no problem. Since the Si-containing photoresist is hardly etched, the consumption of the etching species in the resist portion is small, and the etching rate of polyetheramide is improved accordingly. Processing was completed in about 1/3 of the time when a conventional resist was used. After the etching, the resist was peeled off, and the etched surface was observed with an SEM. As a result, the etching was satisfactory without generation of fine spot-like residues.

When the polyetheramide resin is used as the protective layer as in this embodiment (when the etching area is small), one wafer processing to four wafer processing / batch is performed under the same conditions as five wafer processing / batch. However, etching could be performed. This is because the silicon-containing resist is hardly etched and does not affect the etching characteristics unlike the novolak-based positive resist, so that etching can be performed under the same conditions for processing one to five wafers. In addition to the above-mentioned Si-containing photoresist, there is also a negative resist. For example, SNR manufactured by Tosoh Corporation
(Silicon-based negative resist).

Embodiment 5 In Embodiment 5, the dry etching method of Embodiment 4 described above was applied to an ink jet head. In the present embodiment, a protective film as an ink-resistant layer made of a polyetheramide resin layer was formed on a substrate of an ink-jet head including a heating section formed on the substrate and a heating section formed by the cavitation-resistant layer. . At this time, as a polyether amide resin, for example, HIMAL HL-1200 (manufactured by Hitachi Chemical Co., Ltd.) is applied at 2 μm, patterned by the method of Example 4, and an opening is formed in the protective layer on the heat acting portion by etching. did. When this part was observed by SEM after etching, no residue was generated by etching on the cavitation-resistant layer forming the heat acting part. Next, an ink discharge port and an ink supply port where the ink discharge amount was 8 pl were formed, and the bubbling state and discharge state of the heater were observed and printing was checked. No abnormalities were seen.

In the above description, the case where the etching method of the present invention is applied particularly to an ink jet head has been described. However, the present invention is not limited to this. Have the same effect.

[0039]

As described above, according to the present invention,
For example, by using a polyether amide resin layer as a mask when etching a substrate constituting an ink jet head, defects such as pinholes generated in the mask when the mask is formed can be reduced. Further, according to the present invention, by using a mask having a two-layer structure in which an organic resin layer is formed on a dielectric layer as the mask, it is possible to reduce the above-described defects, and, for example, to improve the precision in anisotropic etching. Good etching can be performed. As a result, an inkjet head can be manufactured with high accuracy and high yield, and as a result, a reliable and inexpensive inkjet recording head can be provided. Further, according to the etching method of the present invention, the patterning of the polyetheramide resin layer can be performed with high throughput and high accuracy, and without increasing the temperature of the substrate without generating etching residues. In the dry etching method for a polyetheramide resin layer of the present invention, by using a silicon-containing photoresist as an etching mask, it is possible to eliminate the generation of fine etching residues and to improve the productivity of photolithography. be able to. In addition, by applying the dry etching method of the present invention using the silicon-containing photoresist as an etching mask to a dry etching apparatus using a plasma excitation method using a microwave discharge of a batch type (a plurality of wafers is processed), It is possible to significantly improve the productivity of the patterning as compared with the case of (1).
Therefore, according to the present invention, while utilizing the properties of the polyether amide resin, and in which fine patterning is required, for example, a protective layer as an ink-resistant layer of an ink jet recording head, or protection of a thermal print head It can be used as a film or a protective film for a semiconductor device, and the reliability of these devices can be improved.

[Brief description of the drawings]

FIGS. 1A to 1D are diagrams showing a configuration of an ink jet head according to a first embodiment of the present invention; FIG. 1B is a cross-sectional view taken along line AA ′ of FIG. 1A; FIG. 3D is a schematic plan view of the Si substrate, and FIG. 4D is a schematic cross-sectional view of the Si substrate.

FIGS. 2A to 2C are schematic diagrams illustrating a manufacturing process of the inkjet head according to the first embodiment of the present invention.

FIGS. 3A to 3C are schematic diagrams illustrating a manufacturing process of an inkjet head according to a second embodiment of the present invention.

FIG. 4 is a schematic cross-sectional view showing an example of anisotropic etching that does not penetrate a substrate.

FIG. 5 is a schematic perspective view illustrating an example of an inkjet printing apparatus that can use an inkjet head manufactured according to a second embodiment of the present invention.

FIG. 6 is a diagram showing a relationship between an etching rate of polyetheramide and a gas composition when an RF 2.45 GHz etching apparatus according to Embodiment 3 of the present invention is used.

FIG. 7 is a diagram showing a relationship between an etching rate of polyetheramide and a pressure when an RF 2.45 GHz etching apparatus according to Embodiment 3 of the present invention is used.

FIG. 8 is a diagram showing a relationship between an etching rate of polyetheramide and an RF output when an RF 2.45 GHz etching apparatus according to a third embodiment of the present invention is used.

FIG. 9 shows RF 13.56 MHz according to the third embodiment of the present invention.
FIG. 4 is a diagram showing a relationship between an etching rate of polyetheramide and a gas composition when using the etching apparatus of FIG.

FIG. 10: A 5-inch wafer is coated and baked with a polyetheramide resin (HIMAL HL-12 manufactured by Hitachi Chemical Co., Ltd.), and is a batch type dry etching apparatus C manufactured by Shibaura Seisakusho.
It is a figure which shows the result of having measured the etching rate using DE-7-4 (microwave power supply).

FIG. 11 is a partial vertical cross-sectional view of an ink-jet head for explaining a configuration of a protective layer as an ink-resistant layer in the present invention.

[Explanation of symbols]

 1: Si substrate 2: Dielectric film 3: Organic resin film 4: Through hole (ink supply port) by anisotropic etching 5: Electrothermal conversion element 6: Discharge port 7: Discharge port plate

Continuing on the front page (72) Inventor Tamaki Sato 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Norio Okuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. F-term (reference) 2C057 AF70 AF93 AP02 AP32 AP34 AQ02 AQ03 (54) [Title of the Invention] An etching method for processing a substrate, a dry etching method for a polyetheramide resin layer, and a method for manufacturing an ink jet recording head , Inkjet head and inkjet printing equipment

Claims (30)

[Claims] An etching method for providing an etching resistant mask having a desired opening pattern on a substrate and performing etching through the etching resistant mask in order to process the substrate. An etching method using an etheramide resin layer. 2. The etching resistant mask has a two-layer structure of a polyetheramide resin layer and a dielectric layer.
The etching method according to claim 1, wherein the polyether amide resin layer is provided on a dielectric layer. 3. The etching method according to claim 1, wherein the opening of the polyetheramide resin layer as the etching resistant mask is formed by dry etching with an etching gas containing oxygen as a main component. Method. 4. The opening of the polyetheramide resin layer as the etching resistant mask is formed by dry etching with an etching gas mainly containing a mixed gas of oxygen and carbon tetrafluoride. The etching method according to claim 1, wherein the etching is performed. 5. The etching method according to claim 1, wherein a silicon wafer is used as said substrate. 6. The etching method according to claim 5, wherein said etching is an anisotropic etching. 7. A dry etching method for a polyetheramide resin layer, wherein the polyetheramide resin layer is
A dry etching method characterized by etching with an etching gas containing oxygen as a main component. 8. A method for dry etching a polyetheramide resin layer, wherein the polyetheramide resin layer is
A dry etching method characterized by etching with an etching gas containing a mixed gas of oxygen and carbon tetrafluoride as a main component. 9. The dry etching method according to claim 1, wherein a silicon-containing photoresist is used as an etching mask for the dry etching.
3. The dry etching method according to 1. 10. A dry etching method in which a plurality of processed objects are buried in the same by plasma excitation using microwave discharge, the plurality of processed objects are etched using the dry etching method according to claim 3. A dry etching method characterized in that: 11. A method for manufacturing an ink jet head for discharging ink, comprising: preparing a substrate constituting an ink jet head, forming a mask pattern comprising a polyetheramide resin layer on the surface of the substrate, A method for manufacturing an ink jet head, comprising: performing an etching process using a pattern as a mask. 12. A method of manufacturing an ink jet head for discharging ink, comprising: preparing a substrate constituting an ink jet head, and forming a polyetheramide resin layer on a dielectric layer on the surface of the substrate. A method for manufacturing an ink jet head, comprising: forming a mask pattern composed of a layer having a layer structure, and performing an etching process using the mask pattern as a mask. 13. The mask pattern according to claim 11, wherein the mask pattern is formed by dry etching using an etching gas containing oxygen as a main component.
3. The method for manufacturing an inkjet head according to item 2. 14. The method according to claim 11, wherein the mask pattern is formed by dry etching using an etching gas mainly containing a mixed gas of oxygen and carbon tetrafluoride. A method for manufacturing an ink jet head. 15. An ink supply port penetrating the substrate by the etching.
15. The method for manufacturing an ink jet head according to any one of items 14 to 14. 16. The method for manufacturing an ink jet head according to claim 11, wherein a silicon wafer is used as said substrate. 17. The ink jet printer according to claim 11, wherein an electrothermal conversion element used for discharging ink and a member for an ink flow path are formed on the substrate. Of manufacturing an inkjet head. 18. The method according to claim 11, wherein the etching is anisotropic etching. 19. A method for manufacturing an ink jet head for discharging ink, comprising preparing a substrate constituting an ink jet head, and forming a protective film as an ink resistant layer made of a polyetheramide resin layer on the surface of the substrate. A method for manufacturing an ink jet recording head, comprising: forming the protective film and processing the protective film by the dry etching method according to claim 7. 20. The method according to claim 20, wherein the protective film is a protective film formed on the substrate including at least a heat acting portion, and the opening of the heat acting portion is processed by etching the protective film. Item 20. The method for manufacturing an ink jet recording head according to Item 19. 21. An ink jet head for discharging ink, wherein a substrate constituting the ink jet head is prepared, a mask pattern made of a polyetheramide resin layer is formed on the surface of the substrate, and the mask pattern is used as a mask. An ink jet head manufactured by a manufacturing method having each step of performing an etching process. 22. An ink jet head for ejecting ink, comprising a substrate constituting an ink jet head, and a two-layer structure in which a polyetheramide resin layer is formed on a dielectric layer on the surface of the substrate. An ink jet head manufactured by a manufacturing method having each step of forming a mask pattern made of a layer and performing an etching process using the mask pattern as a mask. 23. The ink jet head according to claim 19, wherein the mask pattern is formed by the dry etching method according to any one of claims 7 to 9. . 24. An ink supply port penetrating the substrate by the etching.
23. The ink-jet head according to any one of items 22 to 22. 25. An ink jet head according to claim 21, wherein a silicon wafer is used as said substrate. 26. An apparatus according to claim 21, wherein said substrate is formed with an electrothermal transducer and an ink flow path member used for discharging ink. Inkjet head. 27. An ink jet head according to claim 25, wherein said etching is anisotropic etching. 28. An ink jet head for discharging ink, wherein a substrate constituting the ink jet head is prepared, and a protective film as an ink resistant layer made of a polyetheramide resin layer is formed on the surface of the substrate. An ink jet head, wherein the protective film is processed by the dry etching method according to claim 7. 29. An apparatus according to claim 28, wherein said protective film is a protective film formed at least on a heater portion of a head substrate, and an opening surface of said heater portion is processed by etching the protective film. The inkjet head according to the above. 30. An ink jet printing apparatus for performing printing by discharging ink, wherein an ink jet head for discharging ink is constituted by the ink jet head according to any one of claims 21 to 29. An ink-jet printing apparatus, characterized in that: