JP2005206401A - Method of manufacturing structural body, droplet discharge head, and droplet discharge apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce a manufacture cost by shortening the manufacturing time in the formation of holes having different diameters from one another on a glass substrate. <P>SOLUTION: The method of manufacturing a structural body having a plurality of the holes having different diameters from one another includes: a 1st process for forming a plurality of modified areas each having different length in the thickness direction of the glass substrate by irradiating the glass substrate with laser beam and scanning the focus of the laser beam in the thickness direction of the glass substrate; and a 2nd process for forming a plurality of the holes having different diameters from one another along a plurality of the modified areas. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a manufacturing technique of a structure including a glass substrate, and more particularly to a manufacturing technique suitable for manufacturing a fluid device such as a droplet discharge head.

  2. Description of the Related Art In recent years, device development using MEMS (micro electro mechanical systems) technology has been actively performed and applied to the manufacture of various fluid devices such as a droplet discharge head, a biochip, a micropump, and the like. Such a device is composed of, for example, a silicon substrate or a glass substrate, and the substrate includes a plurality of channels for forming a flow path for allowing some liquid to pass through the device and a discharge hole for discharging the liquid to the outside. Holes with different hole diameters are formed.

The process of forming a through-hole or the like in a glass substrate or the like is processing in the thickness direction of the glass substrate or the like, and the processing is often performed by mechanical processing using a cutting tool such as a drill. Recently, as one of the techniques for performing microfabrication on a glass substrate, a difference in etching rate is caused between the light irradiation region and the non-irradiation region by irradiating light on a desired position of the glass substrate. A processing technique for removing the film by etching is known. Such a technique is described in, for example, JP-A-9-309744 (Patent Document 1).
Japanese Patent Laid-Open No. 9-309744

  By the way, in the conventional processing technique, when a plurality of holes having different hole diameters are formed in a glass substrate, for example, when a plurality of through holes are formed by mechanical processing, the processing time becomes long and the entire manufacturing time can be shortened. There was an inconvenience that the manufacturing cost was reduced.

  Further, Patent Document 1 described above does not disclose a method of forming a plurality of holes having different hole diameters, and therefore a technique for solving such a problem is desired.

  Then, an object of this invention is to provide the technique which shortens the manufacturing time at the time of forming the hole of a mutually different hole diameter with respect to a glass substrate, and can aim at reduction of manufacturing cost.

  In order to solve the above-described problem, a first aspect of the present invention is a method for manufacturing a structure having a plurality of holes having different hole diameters, and the glass substrate is irradiated with laser light to focus the laser light on the structure. A first step of forming a plurality of altered regions on the glass substrate having different lengths in the thickness direction of the glass substrate by scanning in the thickness direction of the glass substrate; And a second step of forming a plurality of holes having different hole diameters along the altered region.

  According to this manufacturing method, the etching start time can be controlled by changing the length of the glass substrate in the thickness direction of the altered region and adjusting the thickness of the non-altered region (unirradiated portion) of the laser beam. It becomes possible. Therefore, it is possible to simultaneously manufacture a plurality of holes having different hole diameters without requiring a complicated process. Therefore, the manufacturing cost can be reduced and the mass productivity is excellent.

  In this specification, the “glass substrate” includes substrates made of various kinds of glass such as soda glass, quartz glass, borosilicate glass, and the like. In addition, the “modified region” means that the density, refractive index, mechanical strength, or other physical characteristics are different from the surroundings, and the region is more easily etched than the region other than the modified region (high etching rate). The area that became. The altered region includes those in which minute cracks are generated.

  In the first step, at least one of the altered regions may be formed on the glass substrate so that unmodified regions that are not irradiated with laser light remain on both sides of the altered region. According to this, the etching start time can be adjusted by leaving the non-altered regions on both sides of the glass substrate. Since etching proceeds from both sides, a desired hole can be formed in a shorter time. Further, since etching proceeds from both sides, the hole diameter can be made more uniform at any position than when etching is performed from one side. The altered region may be formed on the glass substrate so that the unaltered regions remain on both sides of all the altered regions. Moreover, the modified | denatured area | region penetrated on the both sides of the glass substrate may be formed.

  In the first step, all the altered regions of the altered region may be formed on the glass substrate such that one end of the altered region is exposed on one surface of the glass substrate. That is, an unaltered region that is not irradiated with laser light may be formed only on one side of the glass substrate. According to this, the etching start time can be adjusted by leaving the non-altered region on one side of the glass substrate.

  It is preferable that after the first step, a step of covering the surface side of the altered region of the glass substrate where one end of the altered region is exposed with an etching protective film is included. Thereby, the advancing surface of the etching of the glass substrate can be reliably determined on one side.

  The laser beam is preferably a pulsed laser beam. This makes it possible to minimize unnecessary energy application to a portion other than the region where the altered region of the glass substrate is to be formed.

  The pulse laser beam is preferably a femtosecond laser beam. As a result, the altered region can be locally formed, and finer holes can be formed. Here, “femtosecond laser light” refers to laser light having a pulse width on the order of femtoseconds (for example, several tens to several hundreds femtoseconds).

  The second aspect of the present invention is a device using the structure manufactured by the above manufacturing method. Here, the “device” includes a droplet discharge head (inkjet head), a microfluidic chip (electrophoresis chip, microreactor, etc.), a biosensor, an electroosmotic flow pump, and the like.

  A third aspect of the present invention is a droplet discharge apparatus (inkjet apparatus) configured to include a droplet discharge head as the device.

  A fourth aspect of the present invention includes a plurality of storage units that store various types of liquids, and a plurality of discharge holes that individually discharge the liquid supplied from each of the storage units. The droplet discharge heads have different diameters depending on the flow characteristics of the liquid stored in the storage portion.

  According to this, since a plurality of holes having a hole diameter corresponding to the flow characteristics of the liquid to be discharged are provided, it is possible to reduce variation in the discharge amount even when discharging a plurality of types of liquid having different flow characteristics. Become.

  Embodiments of the present invention will be described in detail with reference to the drawings. Hereinafter, a manufacturing method thereof will be described by taking a structure used as a component of a droplet discharge head as an example.

(First embodiment)
1 and 2 are process diagrams for explaining a structure manufacturing method. 1 and 2 illustrate a process of forming a plurality of holes (through holes) having different hole diameters on a glass substrate.

  First, as shown in FIG. 1A, the laser beam 12 is irradiated from one surface side of the glass substrate 10 to a first through-hole formation scheduled site 13a (shown by a dotted line in the figure) which is a site where a through-hole is to be provided. By irradiating and scanning the focal point of the laser beam 12 in the thickness direction of the glass substrate 10, an altered region 14a (indicated by a thick line in the figure) extending in the thickness direction of the glass substrate 10 is formed. The irradiation with the laser beam 12 is performed corresponding to a position where the through hole is to be formed in the glass substrate 10. In this example, the altered region 14a is formed from one surface of the glass substrate 10 to the other surface.

  Next, similarly, the non-irradiated portions (non-altered regions) are left in the second through-hole formation scheduled site 13b and the third through-hole planned site 13c, and the altered regions 14b and 14c having different depths are formed. To do.

  As described above, by changing the depth of the altered region by the laser beam 12 and providing an unirradiated portion having various thicknesses, it is possible to shift the start time of the etching process in a later process.

  Here, as the glass substrate 10, it is possible to use substrates made of various glasses such as soda glass, quartz glass, borosilicate glass, and the like. Further, when a glass substrate made of an alkali ion such as sodium or lithium, for example, a glass substrate made of silicate glass, borosilicate glass, aluminosilicate glass, phosphate glass, or the like is used as the glass substrate 10, this glass substrate is later used. An anodic bonding method can be used conveniently when it is desired to bond 10 to a semiconductor substrate, a metal substrate, or the like.

  The “altered region” refers to a region where the density, refractive index, mechanical strength, or other physical characteristics are different from the surroundings, and includes those in which minute cracks are generated.

  As the laser beam 12, various types can be adopted as long as the altered region 14 can be formed on the glass substrate 10. Further, any means other than the laser beam can be adopted as long as it is possible to apply energy to a desired position of the glass substrate 10 by electron beam irradiation or the like. In the present embodiment, a femtosecond laser beam having a pulse width of femtosecond order (for example, several tens to several hundreds femtoseconds) is used as a preferable example of the laser beam 12. For example, femtosecond laser light having a wavelength of 800 nm, a pulse width of 100 fs (femtosecond), and a repetition frequency of 1 kHz is used.

When femtosecond laser light is irradiated, the energy density is extremely high in the vicinity of the condensing point, and large energy can be injected locally instantaneously. In the portion irradiated with the femtosecond laser beam, various microscopic structural changes are induced by various nonlinear interactions (for example, multiphoton absorption multiphoton ionization, etc.) between the laser beam and the substance constituting the glass substrate 10. Is done. The induced structural change depends on the intensity of the laser beam, and (a) coloring by oxidation-reduction of active ions (rare earth, transition metal, etc.), (b) refractive index change by defect purification and densification, (c) melting And void formation by a laser shock wave, (d) formation of a micro crack by an optical breakdown, and the like. In many cases, the induced structural changes are complex and have a certain spatial distribution. Of these structural changes, the present embodiment mainly uses the microcracks described in (d) above. This microcrack is induced by a phenomenon (breakdown) in which stress distortion occurs in the vicinity of the focal point. When femtosecond laser light is used, the pulse width is shorter than the coupling time between electrons and phonons (on the order of ^10-12 seconds), so the energy of the laser light is irradiated sufficiently faster than the thermal diffusion rate of the material. The plasma is generated by being injected in a concentrated manner. Cracks are induced by shock waves generated when the plasma diffuses. Therefore, the irradiation conditions (intensity, pulse width, mode, wavelength, etc.) of the laser light 12 are appropriately set according to the material of the glass substrate 10 and other conditions so that microcracks are mainly generated in the glass substrate 10. As a result, the altered region can be formed only in an extremely fine region, and fine processing can be achieved.

  Next, as shown in FIG. 1B, the laser beam irradiation surface side of the glass substrate 10 is covered with an etching protective film 16. The etching protection film 16 is formed using a mask material such as gold (Au), chromium (Cr), polysilicon (Si), or the like.

  Next, the glass substrate 10 is etched. Here, in the step of FIG. 1B, the laser light irradiation surface (surface where all the altered regions are exposed) side of the glass substrate 10 is covered with the etching protective film 16, so that etching is performed on the glass substrate 10. Progressing entirely from the other side, that is, the side opposite to the laser light irradiation surface.

  As shown in FIG. 1C, first, etching proceeds selectively at a high speed from the first through-hole formation scheduled site 13a where the altered region 14a is exposed on the back surface (the other surface), and along the altered region 14a. The region is removed preferentially over the other regions, and a small V-shaped hole is formed. At the same time, the entire surface etching proceeds slowly. Thereafter, as shown in FIG. 1D, when the entire surface etching proceeds to reach the altered region 14b formed in the second through-hole formation planned portion 13b, the second through-hole formation planned portion 13b also Etching at a high speed along the altered region 14b proceeds to form a substantially V-shaped small hole. At this time, the hole further expands and becomes large at the first through-hole formation scheduled site 13a. Further, when the entire surface etching reaches the altered region 14c of the third through-hole formation scheduled site 13c, selective high-speed etching along the altered region 14c is started as shown in FIG. In this way, by forming an altered region having various depths while leaving an unirradiated portion, the timing at which selective high-speed etching is started can be shifted, and a plurality of holes having different hole diameters can be formed simultaneously. Is possible. Note that in FIGS. 1C, 1D, and 2E, a dotted arrow indicates a direction in which etching is performed.

  Etching is stopped when each through-hole reaches a desired size, and the etching protective film 16 is removed, whereby a plurality of tapered (substantially V-shaped) hole diameters as shown in FIG. A structure having a through hole is completed. FIG. 3 shows a schematic view of the completed structure as viewed from above.

  Here, as the etching in this step, wet etching using a hydrofluoric acid solution, dry etching using a fluorine compound gas, or the like can be employed. In addition, the difference in relative hole diameter between the holes is determined by the depth of the altered region, that is, the thickness (depth, distance) of the unirradiated portion as described above, but the absolute hole diameter of each hole is an etching process. Can be adjusted by time.

  Further, as described above, the altered region 14 is mainly composed of microcracks, so that in this step, the etching solution or the etching gas can easily permeate along the thickness direction of the glass substrate 10. As a result, a high etching selectivity can be realized, and a through hole with a smaller hole diameter can be obtained.

  FIG. 4 is a top view schematically illustrating an example of a droplet discharge head used in the present invention. FIG. 5 is a sectional view for explaining a section of the droplet discharge head along points a to j in FIG. A droplet discharge head 100 shown in FIGS. 4 and 5 is a device for discharging a desired liquid by controlling it to a minute amount using an electrostatic actuator, and includes a structure manufactured by the above-described manufacturing method. Consists of.

  As shown in FIGS. 4 and 5, in the droplet discharge head 100 used in the present invention, the glass substrate 10 described above is used as a nozzle substrate, and four more substrates 26, 28, 30, 32 has a laminated structure. A head unit 110 for discharging liquid to the outside is configured from the substrates 10, 26, and 28, and a storage unit 120 for storing liquid supplied to the head unit from the substrates 30 and 32 is configured.

  As the board | substrates 30 and 32 which comprise the accommodating part 120, what processed the resin substrate is used, for example. The substrate 32 is provided with a plurality of storage chambers 40 for storing various types of liquids (sample solutions). Further, the substrate 30 and the substrate 32 form a fine flow path 36 for supplying the sample solution stored in the storage chamber 40 to the pressurizing chamber 34 provided in the head portion 120.

  FIG. 10 is a perspective view showing an example of the head unit 110, and FIG. 11 is a top view for explaining the mechanism of the head unit 110.

  As shown in FIGS. 10 and 11, the head unit 110 includes substrates 10, 26, and 28. As the substrates 26 and 28, for example, processed semiconductor substrates are used. In the substrate 28, supply ports 37 for supplying the sample solution from the storage chamber 40 to the pressurizing chamber 34 provided in the substrate 26 are formed in a staggered manner. The sample solution supplied from the supply port 37 is carried to each pressurizing chamber 34 via a flow path 36 formed in the substrates 26 and 28. In addition, an electrode 38 made of an ITO film or the like is formed on the substrate 28 in a groove formed at a position facing the pressurizing chamber 34. An output power source from an external power source (not shown) is applied between the electrode 38 and an electrode (not shown) provided on the substrate 26 via a connection terminal 42, so that the bottom of the pressurizing chamber 34 is applied. The provided diaphragm 35 is attracted to the electrode 38 and elastically deformed. Thereafter, when the voltage is released, the sample solution supplied to the pressurizing chamber 34 is ejected as droplets from the nozzle hole 22 by the restoring force of the vibration plate 35 to return to the original position. The nozzle hole 22 includes the above-described holes 22a, 22b, and 22c.

  FIG. 6 is a diagram (perspective view) for explaining an example of a droplet discharge apparatus configured using the above-described droplet discharge head. A droplet discharge device 500 shown in FIG. 6 includes a table 510, a Y direction drive shaft 520, a droplet discharge unit 300, an X direction drive shaft 530, a drive unit 540, and a control computer 600. This droplet discharge device is used, for example, for manufacturing a microarray (biochip) used for biotechnology-related inspections and experiments.

  The table 510 is for mounting a substrate constituting the microarray. The table 510 can mount a plurality of substrates, and is configured to be able to fix each substrate by, for example, vacuum suction.

  The Y-direction drive shaft 520 is for freely moving the table 510 along the Y direction shown in the figure. The Y-direction drive shaft 520 is connected to a drive motor (not shown) included in the drive unit 540, and moves the table 510 by obtaining a drive force from the drive motor. The X direction drive shaft 530 is for freely moving the droplet discharge unit 300 along the X direction shown in the figure. The X-direction drive shaft 530 is connected to a drive motor (not shown) included in the drive unit 540, and moves the droplet discharge unit 300 by obtaining a drive force from the drive motor.

  The droplet discharge unit 300 discharges the biomolecule solution toward the substrate based on the drive signal supplied from the control computer 600, and the nozzle surface for discharging the solution faces the table 510. The directional drive shaft 530 is assembled. The droplet discharge unit 300 uses the droplet discharge head 100 driven by the electrostatic driving method described above as a head for discharging a solution. The electrostatic drive type inkjet head has a relatively simple structure, stable solution discharge, and does not use heat, so it can avoid deterioration of biomolecules in the solution and maintain its activity. It becomes. In addition, the apparatus can be reduced in size and power consumption.

  The drive unit 540 includes a motor and other drive mechanisms that drive the Y-direction drive shaft 520 and the X-direction drive shaft 530, respectively. By operating these motors and the like based on drive signals supplied from the control computer 600, the relative position between the table 510 on which the substrate is placed and the droplet discharge unit 300 is controlled. The control computer 600 is installed in the housing of the drive unit 540, and controls the operation of the droplet discharge unit 300 (solution discharge timing, number of discharges, etc.).

  As described above, according to the manufacturing method of the present embodiment, the depth of the altered region formed by irradiating the laser beam 12 is adjusted, and the thickness of the unirradiated portion where the laser irradiation is not performed is adjusted to various thicknesses. Thus, the etching start time can be controlled. Therefore, it is possible to simultaneously manufacture a plurality of holes having different hole diameters without requiring a complicated process. Therefore, the manufacturing cost can be reduced and the mass productivity is excellent. In addition, since a processing method that utilizes the effect of the difference in the irradiation depth of the laser beam 12 is adopted, it is not necessary to form a photoresist on the glass substrate 10, and a plurality of holes having different hole diameters can be easily formed. It becomes possible. In addition, since the hole is formed by the etching process, the hole having a smooth surface can be formed. Therefore, in particular, when a structure is used as the nozzle substrate of the droplet discharge head, no step is generated in the nozzle hole, so that bubbles generated in the head can be discharged outside without being trapped. Therefore, it is possible to reduce fluctuations in ejection characteristics due to bubbles.

  In addition, according to the present embodiment, it is possible to easily create a droplet discharge head including a plurality of nozzle holes having different hole diameters. Therefore, it is possible to easily manufacture holes having different hole diameters according to the flow characteristics of the discharged liquid. When a droplet discharge head having different hole diameters according to the flow characteristics of the discharge liquid is used, it is possible to reduce variations in discharge amount even when discharging a plurality of types of liquids having different flow characteristics. As a result, even when a biochip such as a microarray is produced, the spot diameters can be easily made uniform. Further, since the nozzle substrate is formed of a glass substrate, it is possible to observe the pressure chamber of the droplet discharge head from the outside.

  In the above-described embodiment, the direction in which etching proceeds is determined by covering the laser beam irradiation surface side of the glass substrate 10 with the etching protective film, but the present invention is not limited to this. That is, for example, when the glass substrate 10 is infiltrated into the etching solution, the etching protective film may not be provided if the etching solution can be prevented from touching the laser light irradiation surface side. Further, the etching protective film may not be provided even when the etching traveling direction can be selectively controlled by spraying the etching liquid or the etching gas from the side opposite to the laser light irradiation surface of the glass substrate 10.

  In addition, the etching protective film 16 is formed after the laser beam 12 is irradiated in the above example, but the present invention is not limited to this, and may be formed before the laser beam 12 is irradiated.

  In the above-described embodiment, etching is performed until a through hole is generated. However, the etching may be stopped before the through hole is generated, and the glass substrate may be cut at an arbitrary position to form a through hole.

  In the above-described embodiment, a liquid droplet ejection head (inkjet head) has been described as an example of a device using the structure according to the present invention. In addition, a microfluidic chip (electrophoresis chip, The present invention can be applied to the production of various devices such as microreactors and the like, biosensors, electroosmotic flow pumps and the like.

  In this embodiment, the electrostatic drive system is exemplified as the droplet discharge head. However, the present invention is not limited to this, and a piezoelectric drive system using a piezoelectric element may be used.

  Further, the laser irradiation direction is not particularly limited as long as the altered region can be formed at a desired position.

(Second Embodiment)
8 and 9 are process diagrams for explaining a method for manufacturing a structure according to another embodiment. In the first embodiment, the holes 22 a to 22 c are formed by leaving an unirradiated portion of the laser light 12 on one side of the glass substrate 10 and performing etching from the unirradiated portion side. On the other hand, in this embodiment, as shown in FIG. 8A, the unirradiated portion of the laser beam 12 is left on both sides of the glass substrate 10 and etching is performed from both sides.

  As a result, the etching proceeds as shown in FIGS. 8B to 8C and FIG. 9D, and finally the hole diameter having a substantially X-shaped cross section as shown in FIG. 9E is different. Holes 22a to 22c are formed.

  According to the present embodiment, the etching start time can be adjusted by leaving the unirradiated portions (non-altered regions) of the laser light on both sides of the glass substrate. In addition, since the etching process proceeds from both sides of the glass substrate, it is possible to obtain holes having different desired hole diameters faster than when the etching process is performed from one side. According to this, since etching proceeds from both sides, a desired hole can be formed in a shorter time. Further, since etching proceeds from both sides, the hole diameter can be made more uniform at any position than when etching is performed from one side.

  Next, this invention is demonstrated based on an Example.

  A glass substrate made of Pyrex (registered trademark) glass having a thickness of about 1 mm was irradiated with laser light according to the following laser light irradiation conditions. After the laser beam irradiation surface (surface where the altered region is exposed) of this glass substrate was protected with an etching protective film, it was immersed in a 3% hydrofluoric acid solution for 90 hours to form five nozzle holes having different diameters.

Table 1 below and FIG. 7 show the relationship between the thickness (distance) of the laser non-irradiated portion and the nozzle hole diameter. FIG. 7 is a graph of the data in Table 1. In addition, the nozzle hole diameter measured the hole diameter of the minimum part here.
(Laser irradiation conditions)
Laser light source: Ti-sapphire Wavelength: 800nm
Pulse width: 100 fs
Repeat frequency: 1kHz
Laser power: 10mW
Scan speed: 0.5mm / s
Numerical aperture (NA): 0.8

表１及び図７に示すように、レーザ未照射部とノズル孔径の変化量はほぼ比例しており、レーザ未照射部の距離を調整することで、所望の孔径の孔が精度よく得られることが理解される。

As shown in Table 1 and FIG. 7, the amount of change in the laser non-irradiated part and the nozzle hole diameter is almost proportional, and by adjusting the distance between the laser non-irradiated part, a hole with a desired hole diameter can be obtained with high accuracy. Is understood.

FIG. 1 is a process diagram for explaining a manufacturing method of an example of a structure. FIG. 2 is a process diagram for explaining an example of the manufacturing method of the structure. FIG. 3 shows a schematic view of the structure as viewed from above. FIG. 4 is a top view schematically illustrating an example of a droplet discharge head used in the present invention. FIG. 5 is a sectional view for explaining a section of the droplet discharge head along points a to j in FIG. FIG. 6 is a diagram (perspective view) for explaining an example of a droplet discharge apparatus configured using the above-described droplet discharge head. FIG. 7 is a diagram showing the relationship between the thickness (distance) of the laser non-irradiated part and the nozzle hole diameter. FIG. 8 is a process diagram for explaining a structure manufacturing method according to another embodiment. FIG. 9 is a process diagram for explaining a structure manufacturing method according to another embodiment. FIG. 10 is a perspective view illustrating an example of the head unit. FIG. 11 is a top view for explaining the mechanism of the head unit.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Glass substrate, 12 ... Laser beam, 13a, 13b, 13c ... Through-hole formation plan part, 14a, 14b, 14c ... Alteration area | region, 16 ... Etching protective film, 18 ... Laser light, 22a, 22b, 22c ... (nozzle) holes, 26, 28, 30, 32 ... substrate, 34 ... pressurizing chamber, 35 ... diaphragm, 36 ... flow path , 38 ... Electrode, 40 ... Storage chamber, 100 ... Droplet discharge head, 300 ... Droplet discharge unit, 500 ... Droplet discharge device, 600 ... Control computer

Claims (9)

A method for producing a structure having a plurality of holes having different hole diameters,
A plurality of altered regions having different lengths in the thickness direction of the glass substrate are formed on the glass substrate by irradiating the glass substrate with laser light and scanning the focal point of the laser light in the thickness direction of the glass substrate. The first step;
A second step of etching the glass substrate to form a plurality of holes having different hole diameters along the plurality of altered regions;
A structure manufacturing method comprising:   The said 1st process WHEREIN: At least 1 alteration region of the said alteration region is formed in the said glass substrate so that the unaltered region which a laser beam may not irradiate on both sides of the said alteration region remains. Method for manufacturing the structure.   2. The structure according to claim 1, wherein in the first step, all of the altered regions of the altered region are formed on the glass substrate such that one end of the altered region is exposed on one surface of the glass substrate. Manufacturing method.   The manufacturing method of the structure of Claim 3 including the process of coat | covering the surface side which the one end of the said alteration region of the said glass substrate exposed before the said 2nd process with an etching protective film.   The structure manufacturing method according to claim 1, wherein the laser beam is a pulsed laser beam.   The structure manufacturing method according to claim 5, wherein the pulse laser beam is a femtosecond laser beam.   A droplet discharge head using the structure manufactured by the manufacturing method according to claim 1.   A droplet discharge apparatus comprising the droplet discharge head according to claim 7. It has a plurality of storage parts for storing various types of liquids, and a plurality of discharge holes for individually discharging the liquid supplied from each of the storage parts, and the hole diameters of the plurality of discharge holes are in the storage part A liquid droplet ejection head, which differs depending on the flow characteristics of the liquid to be stored.

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