JP2015010933A - Manufacturing method of cell for liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cell for liquid excellent in analysis accuracy in terahertz spectroscopic measurement.SOLUTION: A manufacturing method of a cell for liquid constituted of a tabular first window member, a space member and a second window member has a constitution including a first window member side metal film formation step (S1), a space member side metal film formation step (S2), a member bonding step (S3), a measuring object inclusion space formation step (S4), a whole resist film peeling step (S5), a second window member side metal film formation step (S6) and a whole member bonding step (S7).

Description

  The present invention relates to a liquid cell used in a spectroscopic device for measuring a transmitted waveform.

  In recent years, terahertz waves in the boundary region between light and radio waves have attracted attention and are used for analysis in various fields. As an analysis method, a terahertz spectrometer is used. This terahertz spectrometer can measure gases, solids, powders, liquids, etc., irradiates the object to be measured with terahertz pulse waves, and performs Fourier transform on the waveform data of the terahertz pulse waves transmitted from the object to be measured This is a spectroscopic method for obtaining the amplitude and phase for each frequency. In the terahertz spectroscopic measurement, when the material of the object to be measured is solid, it is measured by forming a flat plate, and when the material is powder, it is measured by tableting with a tablet molding machine. Further, when the material of the object to be measured is gas, the measurement is performed by sealing the object to be measured in a container called a gas cell. In the case of liquid, it is measured by being enclosed in a container called a liquid cell. The liquid cell is made of a transmissive device such as synthetic quartz glass, crystal, or high-resistance silicon wafer, and is formed to transmit a terahertz pulse wave. The liquid cell is formed with a space for enclosing the object to be measured having a certain distance between two permeable devices. The liquid cell is guided to inject the object to be measured into the space for enclosing the object to be measured. A liquid mouth portion is provided. Since water has the property of absorbing and preventing transmission of terahertz waves, the object to be measured is sealed in a liquid cell formed with a short optical path length in the direction of irradiating the object to be measured with terahertz pulse waves. Measured.

  Next, a method for manufacturing a liquid cell will be described. In the method for manufacturing a liquid cell, a metal film is formed on one main surface of the permeable device. Next, a resist film is formed on the surface of the metal film provided on the permeable device. Next, a desired shape is drawn by irradiating the resist film with light or an electron beam. Next, the metal film is etched in the shape of the portion that is drawn and exposed on the resist film. Next, the transparent device exposed by etching the metal film is etched. Next, the resist film and the metal film are peeled off from the etched exposure apparatus. Next, a liquid cell is formed by laminating permeable devices and bonding them together (see, for example, Patent Document 1).

JP 2009-288046 A

However, since the space in which the object to be measured is enclosed in the conventional liquid cell is formed by etching, the depth of the space in which the object to be measured is enclosed, the residue, etc. are generated depending on the progress of the etching. was there. Therefore, the distance in the transmission direction of the object to be measured for terahertz spectroscopic measurement varies. Therefore, when terahertz spectroscopic measurement is performed, the waveform data of the terahertz pulse wave transmitted from the object to be measured causes an error and causes the analysis accuracy of the object to be deteriorated.
Therefore, an object of the present invention is to provide a liquid cell that solves the above problems and has excellent analysis accuracy in terahertz spectroscopy measurement.

  According to the present invention, there is provided a liquid cell manufacturing method including a plate-like first window member, a space member, and a second window member, wherein the first window member is formed on one main surface of the first window member. A first window member side metal film forming step of forming a side metal film, and forming a space member side first metal film on one main surface of the space member and a space member side second metal film on the other main surface of the space member. Forming a resist film on the surface of the space member side second metal film provided on the other main surface of the space member; and forming a resist film on the surface of the space member side second metal film provided on the other main surface of the space member. Then, the space member-side first provided on one main surface of the space member from the space member-side second metal film in the shape of the exposed space member-side second metal film by peeling off the exposed resist film with a predetermined outer shape pattern. A process for forming a space to be measured that etches up to a metal film, and a resist that completely removes the resist film The peeling step, the second window member-side metal film forming step for forming the second window member-side metal film on one main surface of the second window member, the first window member, the space member, and the second window member are joined. And an all-member joining step for etching the first window member side metal film and the second window member side metal film in the measured object enclosure space.

  In addition, the liquid cell manufacturing method includes a plate-like first window member and a space member, and the first window member-side metal film is formed on one main surface of the first window member. Member-side metal film forming step, space member-side first metal film forming step for forming the space member-side first metal film on one main surface of the space member, and member joining step for joining the first window member and the space member A resist film is formed on the surface of the other main surface of the space member, and the resist film exposed in a predetermined outer shape pattern is peeled off to be exposed from the space member to the one main surface of the space member. The object-containing space forming step for etching up to the first metal film on the space member side, the entire resist film removing step for removing all the resist film, and the first window member and the space member are joined to each other in the object-containing space All member joining steps for etching the first window member side metal film In is configured.

  According to the present invention, the direction in which the terahertz pulse wave in the portion where the measurement object is sealed in the liquid cell, that is, the direction in which the optical path length is short, is a space from the main surface of the first window member to which the space member is joined. It becomes to the main surface of the 2nd window member to which the member was joined. Therefore, it has the same distance from the main surface of the 1st window member to which the space member was joined to the main surface of the 2nd window member to which the space member was joined. Therefore, the space in which the object to be measured is enclosed in the liquid cell of the present invention is formed with less variation in the distance in the direction in which the optical path length is shorter than the method of forming the space in which the object to be measured is sealed by conventional etching. be able to. Further, the terahertz spectroscopic measurement can perform measurement with improved analysis accuracy of the object to be measured.

It is a flowchart explaining the manufacturing process of the cell for liquids in the 1st Embodiment of this invention. It is a figure which shows the manufacturing process of the cell for liquid in the 1st Embodiment of this invention, (a) is a figure which shows the state which formed the 1st window member side metal film in the 1st window member, (b) FIG. 6 is a view showing a state in which a space member side first metal film is formed on one main surface of the space member and a space member side second metal film is formed on the other main surface of the space member, and (c) is a first window member. And (d) shows a state in which a resist film is formed on the surface of the second metal film on the space member side and the resist film exposed with a predetermined outer shape pattern is peeled off and peeled off and exposed. It is a figure which shows the state which etched from the space member side 2nd metal film to the space member side 1st metal film in the shape of the made space member side 2nd metal film, (e) is a figure which shows the state which peeled all the resist films (F) is a state in which the second window member-side metal film is formed on one main surface of the second window member. (G) is the state which joined the 1st window member, the space member, and the 2nd window member, and etched the 1st window member side metal film and the 2nd window member side metal film in the to-be-measured object enclosure space FIG. It is a flowchart explaining the manufacturing process of the cell for liquids in the 2nd Embodiment of this invention. It is a perspective view which shows the cell for liquid in the 2nd Embodiment of this invention.

  Hereinafter, some exemplary embodiments of the present invention will be described with reference to the drawings. In addition, the same code | symbol is attached | subjected to the same element and the overlapping description is abbreviate | omitted. In addition, the illustration is exaggerated for the sake of clarity. In addition, the main surface in this embodiment is the widest surface and the plane parallel to it in the three-dimensionally formed crystal plate, for example.

(First embodiment)
As shown in FIGS. 1 and 2, the liquid cell manufacturing method according to the first embodiment of the present invention includes a plate-like first window member 10, a space member 20, and a second window member 30. In the liquid cell 100 configured, the first window member-side metal film forming step (S1), the space member-side metal film forming step (S2), the member joining step (S3), the measured object enclosure space forming step ( S4), the entire resist film peeling step (S5), the second window member side metal film forming step (S6), and the all member joining step (S7). The joining method in the member joining step (S3) and the all member joining step (S7) is performed by an atomic diffusion joining method. In addition, by the method for manufacturing a liquid cell in the first embodiment, the measurement object for sealing the object to be measured for terahertz spectroscopy by sandwiching the space member 20 between the first window member 10 and the second window member 30. An object enclosure space 40 is provided.

First, components of the liquid cell will be described.
The first window member 10 is formed in a transparent flat plate shape made of, for example, artificial quartz or colorless and transparent natural quartz, and the front and back main surfaces of the first window member 10 are formed in parallel.

  Similar to the first window member 10, the second window member 30 is formed in a transparent flat plate shape made of, for example, artificial quartz or colorless and transparent natural quartz, and the front and back main surfaces of the second window member 30 are formed in parallel. ing. The second window member 30 is provided with a liquid introduction port (not shown) through which the measurement object for terahertz spectroscopy measurement is poured into the measurement object enclosure space 40 for terahertz spectroscopy measurement.

  The liquid introduction port portion (not shown) is a through-hole that is provided in the second window member 30 and that pours the measured object into and into the measured object enclosure space 40 for terahertz spectroscopy measurement. In addition, the through hole is relatively opposite to the main surface where the portion of the second window member 30 that becomes the measured object enclosure space 40 is provided, and the main surface of the second window member 30 where the portion of the second window member 30 becomes the measured object enclosure space 40. It penetrates to the main surface of the second window member 30. Further, the liquid introduction port portion (not shown) is formed by two holes, a hole for supplying the object to be measured to the object to be measured enclosure space 40 and a hole for discharging the object to be measured from the space in which the object to be measured is enclosed. Has been.

  The space member 20 is formed in a flat plate shape made of, for example, artificial quartz, colorless and transparent natural quartz, synthetic quartz glass, or a high-resistance silicon wafer, and the front and back main surfaces of the space member 20 are formed in parallel.

Next, a manufacturing method of the liquid cell in the first embodiment of the present invention will be described.
[First Window Member Side Metal Film Forming Step (S1)]
As shown in FIGS. 1 and 2A, the first window member side metal film forming step (S1) is a step of forming the first window member side metal film 1 on one main surface of the first window member 10. It is.

  The first window member side metal film 1 is provided on a base metal film such as Cr (chromium), Ni (nickel), Ta (tantalum), or Ti (titanium), and is made of a metal material such as Au (gold). Is formed. In addition, the formation method of the 1st window member side metal film 1 is formed by sputtering method, a vacuum evaporation method, etc., for example.

[Space member side metal film forming step (S2)]
As shown in FIG. 1 and FIG. 2B, the space member side metal film forming step (S 2) includes the space member side first metal film 2 and the other main member of the space member 20 on one main surface of the space member 20. This is a step of forming the space member side second metal film 3 on the surface.

  The space member side first metal film 2 is provided on a base metal film such as Cr (chromium), Ni (nickel), Ta (tantalum), Ti (titanium) and the like, similar to the first window member side metal film 1. , Made of a metal material such as Au (gold). In addition, the formation method of the space member side 1st metal film 2 is formed by sputtering method, a vacuum evaporation method, etc., for example.

  The space member side second metal film 3 is provided on a base metal film such as Cr (chromium), Ni (nickel), Ta (tantalum), Ti (titanium) and the like in the same manner as the space member side first metal film 2. , Made of a metal material such as Au (gold). In addition, the formation method of the space member side 2nd metal film 3 is formed by sputtering method, a vacuum evaporation method, etc., for example.

[Member joining step (S3)]
As shown in FIG. 1 and FIG. 2C, in the member joining step (S3), the first window member 10 and the space member 20 are combined with the first window member side metal film 1 and the space member side first metal film 2. It is the process made to join through. In addition, the joining method of the 1st window member 10 and the space member 20 is performed by the atomic diffusion joining method.

  In the atomic diffusion bonding method, the first window member-side metal film 1 formed on the first window member 10 and the space member-side first metal film 2 formed on one main surface of the space member 20 are brought into close contact with each other. Bonding using diffusion of atoms generated between bonding surfaces under pressure conditions that do not cause plastic deformation as much as possible under temperature conditions below the melting point between the window member side metal film 1 and the space member side first metal film 2 It is a method to do.

[Measurement Object Enclosing Space Formation Step (S4)]
As shown in FIG. 1 and FIG. 2 (d), the measured object enclosure space forming step (S 4) is performed on the surface of the space member side second metal film 3 provided on the other main surface of the space member 20. 5, the resist film 5 exposed with a predetermined outer shape pattern is peeled off, and the space member-side second metal film 3 is etched in the shape of the space member-side second metal film 3 that has been peeled and exposed. In this step, the space member 20 exposed in step 1 is etched, and the space member-side first metal film 2 provided on one main surface of the space member 20 exposed by etching is etched. The space formed by etching is a space in which an object to be measured for terahertz spectroscopy is enclosed. The resist film 5 is made of, for example, a photosensitive organic material, and is formed by a spin coat method, an electrodeposition resist method, a spray coat method, or the like.

  The exposure is to expose the resist film 5 by placing a mask having an outer shape pattern formed on the resist film 5. Thereby, the surface of the resist film 5 is exposed with the external pattern provided on the mask. Further, the mask has the same outer dimensions as the flat plate-like first window member 10, and a portion in which the object to be measured is enclosed is a through hole.

[All resist film peeling step (S5)]
As shown in FIGS. 1 and 2 (e), in the all resist film peeling step (S5), all the resist film 5 remaining in the portion that has not been etched in the measured object enclosure space forming step (S4) is peeled off. It is a process.

[Second Window Member Side Metal Film Forming Step (S6)]
As shown in FIG. 1 and FIG. 2 (f), the second window member side metal film forming step (S 6) is a step of forming the second window member side metal film 4 on one main surface of the second window member 30. It is.

  The second window member side metal film 4 is provided on a base metal film such as Cr (chromium), Ni (nickel), Ta (tantalum), Ti (titanium), like the space member side second metal film 3. , Made of a metal material such as Au (gold). In addition, the formation method of the 2nd window member side metal film 4 is formed by sputtering method, a vacuum evaporation method, etc., for example.

[All-member joining process (S7)]
As shown in FIGS. 1 and 2G, the all-member joining step (S7) is a joining metal in which the first window member 10, the space member 20, and the second window member 30 are formed between the respective members. This is a step of etching the first window member side metal film 1 and the second window member side metal film 4 in the object-to-be-measured object enclosing space 40, which are joined through the film. Further, the joining method of the all-member joining step (S7) is performed by an atomic diffusion joining method. In addition, for example, a fluorine-based plastic tube is inserted into a hole in two liquid introduction ports (not shown) provided in the second window member 30, and the second window member is made of silicon-based adhesive. 30 is airtightly fixed.

  As described above, by configuring the liquid cell manufacturing method according to the first embodiment of the present invention, the direction in which the terahertz pulse wave is irradiated, that is, the optical path length is short in the portion where the object to be measured is enclosed. The direction is a direction in which the space member 20 is sandwiched between the first window member 10 and the second window member 30. In addition, since the front and back main surfaces of the first window member 10, the second window member 30, and the space member 20 are formed in parallel, the measurement is performed from the surface of the first window member 10 where the measurement object is enclosed. The distance to the surface of the 2nd window member 30 of the part into which an object is enclosed becomes a fixed distance. That is, the portion of the liquid cell 100 according to the present invention in which the object to be measured is enclosed is formed with less variation in distance in the direction in which the optical path length is short. Therefore, the terahertz spectroscopic measurement using the liquid cell according to the first embodiment of the present invention can perform measurement with improved analysis accuracy of the object to be measured.

(Second Embodiment)
A liquid cell 200 according to a second embodiment of the present invention will be described with reference to FIGS. In the liquid cell 200 according to the second embodiment of the present invention, a configuration different from the liquid cell 100 according to the first embodiment is that one direction in which the object to be measured is enclosed is opened. . About another structure, it is the same as that of the cell 100 for liquids in 1st Embodiment.

  As shown in FIG. 3, the method for manufacturing a liquid cell according to the second embodiment of the present invention is a method for manufacturing a liquid cell 200 including a plate-like first window member 10 and a space member 20. The first window member side metal film forming step (S11), the space member side first metal film forming step (S12), the member joining step (S13), the measured object enclosure space forming step (S14), The resist film peeling step (S15) and the all member joining step (S16) are included.

[First Window Member Side Metal Film Forming Step (S11)]
As shown in FIG. 3, the first window member side metal film forming step (S <b> 11) is a step of forming the first window member side metal film 1 on one main surface of the first window member 10.

[Space member side first metal film forming step (S12)]
As shown in FIG. 3, the space member side first metal film forming step (S <b> 12) is a step of forming the space member side first metal film 2 on one main surface of the space member 20.

[Member joining step (S13)]
As shown in FIG. 3, the member joining step (S 13) is a step of joining the first window member 10 and the space member 20 via the first window member side metal film 1 and the space member side first metal film 2. It is. In addition, the joining method of the 1st window member 10 and the space member 20 is performed by the atomic diffusion joining method.

[Measurement Object Enclosing Space Formation Step (S14)]
As shown in FIG. 3, in the measured object enclosure space forming step (S14), a resist film 5 is formed on the surface of the main surface of the space member 20 where the space member side first metal film 2 is not provided, A space member provided on one main surface of the space member 20 exposed by this etching is formed by peeling the resist film 5 exposed in the outer shape pattern and etching the space member 20 in the shape of the space member 20 that is peeled and exposed. This is a step of etching the first side metal film 2. Note that the space formed by the etching is a measured object enclosure space 40 in which the measured object of terahertz spectroscopy is enclosed. The resist film 5 is made of, for example, a photosensitive organic material, and is formed by a spin coat method, an electrodeposition resist method, a spray coat method, or the like.

[All resist film peeling step (S15)]
As shown in FIG. 3, the all resist film removing step (S15) is a step of removing all of the resist film 5 remaining in the portion that has not been etched in the measured object enclosure space forming step (S14).

[All members joining step (S16)]
As shown in FIGS. 3 and 4, in the all-member joining step (S 16), the first window member 10 and the space member 20 pass through the first window member side metal film 1 and the space member side first metal film 2. And the first window member side metal film 1 in the measured object enclosure space 40 is etched. Further, the joining method of the all-member joining step (S16) is performed by an atomic diffusion joining method. Further, the liquid cell 200 is formed through the all-member joining step (S16).

  As described above, by configuring the method for manufacturing a liquid cell according to the second embodiment of the present invention, the direction in which the terahertz pulse wave is irradiated, that is, the optical path length is short in the portion where the object to be measured is enclosed. The direction is a direction from one main surface of the first window member 10 to the main surface of the space member 20 facing the main surface of the space member 20 joined to the first window member 10. Further, since the front and back main surfaces of the first window member 10 and the space member 20 are formed in parallel, the portion in which the object to be measured is sealed from the surface of the first window member 10 in the portion in which the object to be measured is sealed. The distance to the main surface of the space member 20 is a constant distance. That is, the portion of the liquid cell 200 according to the present invention in which the object to be measured is enclosed is formed with less variation in distance in the direction in which the optical path length is short. Therefore, the terahertz spectroscopic measurement using the liquid cell according to the second embodiment of the present invention can perform measurement with improved analysis accuracy of the object to be measured.

In addition, this invention is not limited to this, It can change suitably.
For example, as a modification of the first embodiment, before the space member 20 forms the space member side first metal film 2 and the space member side second metal film 3 in the space member side metal film forming step (S2). It may be physically polished.

  Further, for example, as a modification of the second embodiment, the space member 20 is physically polished before forming the space member side first metal film 2 in the space member side first metal film forming step (S12). It may be.

DESCRIPTION OF SYMBOLS 1 1st window member side metal film 2 Space member side 1st metal film 3 Space member side 2nd metal film 4 2nd window member side metal film 5 Resist film 10 1st window member 20 Space member 30 2nd window member 40 Cover Measurement object enclosure space 100,200 Liquid cell

Claims (2)

A method for producing a liquid cell comprising a plate-like first window member, a space member, and a second window member,
A first window member-side metal film forming step of forming a first window member-side metal film on one main surface of the first window member;
A space member side metal film forming step of forming a space member side first metal film on one main surface of the space member and a space member side second metal film on the other main surface of the space member;
A member joining step for joining the first window member and the space member;
The space member-side second exposed by exposing a resist film formed on a surface of the space member-side second metal film provided on the other main surface of the space member and peeling the resist film exposed with a predetermined outer shape pattern. An object enclosing space forming step for etching from the space member side second metal film to the space member side first metal film provided on one main surface of the space member in the shape of a metal film;
A total resist film peeling step for peeling off the resist film;
A second window member side metal film forming step of forming a second window member side metal film on one main surface of the second window member;
An all-member joining step of joining the first window member, the space member, and the second window member to etch the first window member side metal film and the second window member side metal film in the measured object enclosure space. A method for producing a liquid cell, comprising: A method for producing a liquid cell composed of a plate-like first window member and a space member,
A first window member-side metal film forming step of forming a first window member-side metal film on one main surface of the first window member;
A space member-side first metal film forming step of forming a space member-side first metal film on one main surface of the space member;
A member joining step for joining the first window member and the space member;
A resist film is formed on the surface of the other main surface of the space member, and the resist film exposed with a predetermined outer shape pattern is peeled off to expose the one main surface of the space member from the space member in an exposed shape. A space to be measured enclosing space for etching up to the first metal film on the space member side provided in
A total resist film peeling step for peeling off the resist film;
And a liquid joining method including a whole member joining step of joining the first window member and the space member and etching the first window member side metal film in the space to be measured. Cell manufacturing method.

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