JP2015206640A - Sealed space formation member, and system and method for measuring adsorption/desorption of water molecule using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a space formation member capable of promptly supplying a sufficient amount of water molecules that reaches adsorption/desorption equilibrium between a sample and water molecules to the sample.SOLUTION: A sealed space formation member is used for a water molecule adsorption/desorption measurement system for measuring adsorption/desorption between a sample and water molecules included in a humidity control gas contacted with the sample and forms a sealed space including the sample. The sealed space formation member comprises: an introduction port for introducing the humidity control gas into the sealed space so as to blow the humidity control gas to a measurement area from a position facing to a measuring surface portion (a measurement area) of the sample; and an exhaust port for exhausting the humidity control gas in the sealed space to the outside of the sealed space.

Description

  The present invention relates to a sealed space forming member used in a water molecule adsorption / desorption system for measuring adsorption / desorption between a sample and water molecules. For example, a sealed space forming member used in a water molecule adsorption / desorption measurement system that measures adsorption / desorption of a sample and water molecules using RIFS (Reflectometric Interference Spectroscopy), and water molecule adsorption / desorption measurement using the same The present invention relates to a system and a water molecule adsorption / desorption measurement method.

  Water-related physical properties such as water content, water absorption, hygroscopicity, swelling, moisture retention, wettability are storage stability, functionality, environmental stability, bacterial reproduction, biological life of polymer materials and biological materials. It has very important meaning for stability of wearability or size.

  Conventionally, as a means for quantifying water in a material, there has been a means for measuring the difference in mass between a dry state and a wet state as the amount of water, or for quantifying the water contained in the material physically and chemically. However, the adsorption and desorption of water whose abundance and location are constantly changing even under certain conditions cannot be captured. In order to design materials more precisely and accurately grasp the behavior of water in materials, it is necessary to develop an apparatus that can quantify the adsorption and desorption of a small amount of moisture in a short time with high accuracy.

  Non-Patent Document 1 includes a precision electronic balance, a chamber maintained at a constant temperature in order to prevent measurement errors due to temperature changes, and the precision electronics provided below the chamber and through a communication hole. A sample chamber having a sample pan suspended from a balance, a reservoir provided under the sample chamber for storing water, a temperature probe and a humidity probe provided in the sample chamber, and flow control means An apparatus for water adsorption / desorption measurement provided with humidity control means is disclosed. In this device, the humidity in the sample chamber is changed with the temperature of the sample kept constant, and the sample is weighed by a precision electronic balance in the equilibrium state of adsorption and desorption of water molecules with respect to the sample at each humidity. By determining the adsorption isotherm, the adsorption / desorption behavior of water molecules to the sample can be measured.

  However, since the apparatus of Non-Patent Document 1 has a configuration in which the sample pan is suspended in the sample chamber and the sample is weighed, a physical force is applied to the sample pan so that the gas supply does not affect the measurement of the sample. It will be performed to a spatial position that does not reach. For this reason, it is difficult to quickly supply a sufficient amount of water molecules to the sample so as to reach an equilibrium in which the water molecules adsorb and desorb to the sample.

  In Patent Document 1 and Non-Patent Document 2, a film sample formed on the surface of a sensor (quartz crystal unit) using QCM (quartz crystal microbalance) or QCM-D which is an improved method thereof. Discloses a method for analyzing physical properties such as hygroscopicity (swellability). The QCM sensor is a sensor that oscillates by applying an alternating voltage to the electrodes formed on both sides of the quartz plate, and measures the frequency and wavelength. When water molecules are adsorbed to the sample on one electrode surface, The frequency increases with the amount of adsorption, and the oscillating wavelength also shifts to the longer wavelength side.

  The QCM sensors of Patent Document 1 and Non-Patent Document 2 are partitioned by a first space holding a solution and a porous film that allows vapor to pass between the first space. A quartz resonator provided so that the surface of the one electrode is exposed in the second space, and the relative humidity of the second space is from the first space to the porous film. The amount of solution that permeates through the first space into the first space.

  However, in the mechanism provided in the QCM sensor described in Patent Document 1 and Non-Patent Document 2, the supply of water molecules to the sample permeates from the first space to the second space through the porous membrane. Since it is controlled only by the amount of the solution, it is difficult to quickly supply a sufficient amount of water molecules to the sample so as to reach an equilibrium in which the water molecules adsorb and desorb to the sample.

International Publication No. WO2009 / 005452

“DVD Intrinsic-Compact and Economical Dynamic Vapor Sorption System”, [online], 2008, Surface Measurement Systems (SMS) Ltd, [February 10, 2013 search], Internet <URL: http: // www. thesorptionsolution.com/files/DVS%20Intrinsic%20Brochure.pdf> “ANALYSING VAPOR UPTAKE & RELEASE WITH QCM-D”, [online], 2008, Biolin Scientific, [Search February 10, 2013], Internet <http://www.q-sense.com/file/ 18-analyzing-humidity-effects-with-qcm-d-1.pdf>

  The present inventors have already used the RifS system, which is one of the water molecule adsorption / desorption measurement systems, as a sealed space forming member for forming a sealed space that encloses the measurement area where the sample is placed, and has applied humidity to the measurement area. It has been proposed to use a minute flow path to introduce a regulated gas (Japanese Patent Application No. 2013-080306).

  However, in the minute flow path of the sealed space forming member, in order to increase the water supply amount, the supply amount of gas flowing in the direction parallel to the measurement region (flow rate: gas supply volume per unit time) is increased. As a result, the adsorption efficiency of the water molecules in the gas flow to the sample thin film decreases, and the desorption efficiency also increases. Therefore, the present inventors have devised a configuration in which the adsorption efficiency of water molecules is not lowered even if the gas supply amount is increased in order to quickly and efficiently measure the adsorption and desorption of water molecules between moisture and the sample. .

  That is, in view of the above-described problems, the present invention provides a space-forming member that can quickly supply a sufficient amount of water molecules to a sample to reach an equilibrium where water molecules are adsorbed to and desorbed from the sample. The purpose is to provide.

The inventors of the present invention create a vertical flow of gas containing water molecules with respect to the sample, thereby suppressing the desorption of water molecules from the sample and the equilibrium point of adsorption / desorption of water molecules with respect to the sample in a short time. The present invention was found for the first time that it could be done. In addition, it can be used for real-time water molecule adsorption / desorption measurement in which the humidity of the gas supplied to the sample is continuously changed in a short time to measure the adsorption / desorption of water molecules at each humidity continuously. I also found it.
According to the present invention, the following sealed space forming member [1] to [13] and a water molecule adsorption / desorption measurement method are provided.

[1] A sealed space used for a water molecule adsorption / desorption measurement system for measuring adsorption / desorption of a sample and water molecules contained in a humidity control gas brought into contact with the sample, and forming a sealed space containing the sample. An inlet for introducing the humidity control gas into the sealed space so that the humidity control gas is blown to the measurement region from a position facing the measurement surface portion (measurement region) of the sample; A discharge port for discharging the humidity control gas in the space to the outside of the sealed space;
A sealed space forming member comprising:

  [2] The volume of the sealed space is approximately equal to or less than the amount of the humidity control gas supplied to the sealed space during a time interval for measuring adsorption / desorption of water molecules with respect to the sample. The sealed space forming member according to [1], wherein the sealed space forming member is formed as described above.

  [3] The sealed space forming member according to [2], wherein the volume of the sealed space is 1.5 mL to 3.2 mL.

  [4] The sealed space according to any one of [1] to [3], wherein the ratio of the total opening area of the introduction port: the area of the measurement region is 50: 1 to 480: 1. Forming member.

  [5] The introduction port is provided so that the humidity control gas is blown at an angle in a range of 45 ° to 135 ° with respect to the plane of the measurement region. The sealed space forming member according to any one of [4].

  [6] A plurality of the introduction ports are provided, and the opening of the introduction port is at least one of a circle, an ellipse, and a rectangle. A sealed space forming member.

  [7] The sealed space according to any one of [1] to [6], further including a gas guide member that guides an angle supplied to the measurement region of the flow of the humidity control gas introduced from the introduction port. Forming member.

  [8] The sealed space forming member according to any one of [1] to [7], wherein a surface of the sealed space other than the measurement region is covered with a cover member that is more hydrophobic than the sample.

  [9] A water molecule adsorption / desorption measurement system comprising the sealed space forming member according to any one of [1] to [8].

  [10] A sealed space having an inlet and an outlet is formed so as to contain the sample arranged in the measurement region for measuring adsorption / desorption between the sample and water molecules, and the water containing the water molecules from the inlet is formed. A water molecule adsorption / desorption measurement method for introducing moisture gas into the sealed space and measuring adsorption / desorption between the thin film of the sample and the water molecules, wherein the humidity gas is used as a surface portion for measuring the sample. A water molecule adsorption / desorption measurement method comprising a gas introduction step of introducing the gas into the sealed space through the introduction port so as to spray the measurement region from a position facing the (measurement region).

  [11] The water molecule adsorption / desorption measurement method according to [11], wherein the humidity control gas is blown at an angle in a range of 45 ° to 135 ° with respect to a plane of the measurement region. .

  [12] The water molecule adsorption / desorption measurement method according to [12], wherein the humidity control gas is blown at an angle in a range of 70 ° to 110 ° with respect to a plane of the measurement region. .

  [13] The water molecule adsorption / desorption measurement method according to any one of [10] to [12], wherein the adsorption / desorption between the sample and the water molecule is measured by RIfS (reflection interference spectroscopy).

  According to the present invention, a space forming member capable of rapidly supplying a sufficient amount of water molecules to the sample so as to reach an equilibrium in which the water molecules are absorbed and desorbed with respect to the sample, and the water molecule absorption using the space forming member. A desorption measurement system and a water molecule adsorption / desorption measurement method are provided.

FIG. 1 is a diagram showing an entire RIfS measurement system having a sealed space forming member according to the first embodiment of the present invention. In the center of FIG. 1, a partially broken sectional view of the sealed space forming member is shown. FIG. 2 is a view showing a cross section along the flow path direction of the sealed space forming member of FIG. FIG. 3A is a perspective view of the sealed space forming member of FIG. (B) is an exploded perspective view of the sealed space forming member of (A). (C) is the figure which cut the sealed space formation member of (A) along the AA line, and looked at the arrow direction. (D) is the figure which looked at the sealed space formation member of (C) along the BB line and CC line, respectively, and was seen to each arrow direction. FIG. 4 is an enlarged view of the measurement region of FIG. 2, and is a diagram illustrating an angle θ in the gas introduction direction with respect to the measurement region. FIG. 5 is a diagram illustrating a cover member that covers a region other than the measurement region. (A) is the figure which showed the state before attaching a cover member. (B) It is a figure which shows the state after attaching a cover member. 6A to 6E are diagrams showing examples of the shape of the chamber portion of the sealed space forming member. FIGS. 7A to 7G are diagrams showing examples of gas inlets. (A) is a perspective view of the sealed space forming member of the second embodiment according to the present invention. The O-ring is omitted. (B) is a figure which shows the side surface of (A). (C) is a figure which shows the upper surface (upper side in (A)) of (A). (D) is a figure which shows another side surface of (A). FIGS. 8A to 8E are views showing a sealed space forming member and a sensor chip of the RIfS system according to the second to eighth embodiments. It is a figure explaining RIfS measurement. It is a figure explaining the processing flow in a RIfS measurement. It is a figure explaining humidity control in RIfS measurement. 12A is a perspective view of the sealed space forming member of Comparative Example 1. FIG. (B) is the figure which showed the side surface of (A). (C) is the figure which showed the upper surface (front side in (A)) of (A). (D) is the figure which showed another side surface of (A). (E) is the enlarged view of the reaction part which looked at the cross section along the DD line of (C) in the arrow direction. 13A is a perspective view of the sealed space forming member of Comparative Example 2. FIG. (B) is the figure which showed the side surface of (A). (C) is the figure which showed the upper surface (front side in (A)) of (A). (D) is the figure which showed another side surface of (A). (E) is the figure which looked at the cross section along the EE line of (C) in the arrow direction. (A) The result of the RIfS measurement of Examples 1 to 4 is shown. (B) The result of the RIfS measurement of Examples 5 to 8 is shown. (C) The result of the RIfS measurement of Comparative Example 1 is shown. (D) The result of the RIfS measurement of Comparative Example 2 is shown. (E) The result of the RIfS measurement of Comparative Example 3 is shown. (F) shows the results of RIfS measurement in Examples 9-11.

[First Embodiment]
1 and 2 show a RIfS measurement system (water molecule adsorption / desorption measurement system) 100 using the sealed space forming member according to the first embodiment. In the following description, the upper and lower sides are distinguished from each other. However, for the sake of convenience, the upper and lower sides are not substantially distinguished.

  As shown in FIGS. 1 and 2, the RIfS measurement system 100 measures adsorption / desorption between the sample 2 and water molecules contained in the gas brought into contact with the sample 2, and the sample 2 to be measured is fixed. A flat sensor chip 1 having a measurement region 2a, a sealed space forming member 3 that is partially bonded to the surface of the sensor chip 1 to form a sealed space R so as to enclose the measurement region 2a; Humidity control gas delivery means 4 having a function of delivering a gas whose humidity is adjusted to the space R (hereinafter referred to as “humidity control gas”), an exhaust mechanism (not shown) for exhausting the gas flowing into the sealed space R, A temperature / humidity sensor 5 (see FIG. 2) for measuring the temperature and humidity of the sealed space R, a temperature controller 5A for adjusting the temperature of the sensor chip 1, and a sealed space forming member 3 so that one end faces the sealed space R. Fixed second , 2 optical fibers 6, 7, a light source (white light source or the like) 8 disposed at the other end of the first optical fiber 6, and a light reflected by a measurement region disposed at the other end of the second optical fiber 7. It has a spectroscope 9, the humidity control gas delivery means 4, the exhaust mechanism, the temperature controller 5A, the light source 8 and other devices connected to the control device 10 for controlling the operation thereof.

[Enclosed space forming member]
The sealed space forming member 3 is used in the RIfS measurement system 100 as described above. As shown in FIGS. 1 and 2, the sealed space forming member 3 is a recess (hereinafter referred to as “a closed space R”) that forms the sealed space R in a state where the surface of the sensor chip 1 and the sealed space forming member 3 are partially joined. 3a), a groove 11 having a C-shaped cross section (see FIG. 3D) formed on the upper wall of the chamber portion 3a (the portion forming the ceiling of the sealed space R), and communicating with the groove 11 Gas introducing passages 12A and 12B formed in such a manner, a gas guiding member 13 (see FIGS. 1 to 3) provided so as to penetrate the gas introducing passages 12A and 12B and the groove 11, and a chamber portion 3a. Gas discharge passages 14A and 14B (see FIGS. 1 to 3) and the like having discharge ports formed on the inner peripheral wall.

  The material of the sealed space forming member 3 is not particularly limited, and for example, polydimethylsiloxane (PDMS), acrylic resin, or the like can be used. At least the surface portion inside the chamber portion 3a that forms the sealed space R is a hydrophobic polymer such as a polyolefin resin, a polystyrene resin, an acrylic resin from the viewpoint of not affecting the measurement of water adsorption / desorption. It is preferable to use resins, ABS resins, polysiloxanes and the like.

  Further, the sealed space forming member 3 is, for example, the entire surface of the sealed space forming member 3 is covered with a light-shielding film or does not adversely affect the measurement of the polymer so that unintended light does not enter the sealed space R in the RIfS measurement. A light-shielding material may be selected.

(Chamber (recess))
The volume of the chamber portion 3a of the sealed space forming member 3 is determined based on the flow rate (eg, L / min) of the humidity control gas introduced into the sealed space R by the humidity control gas delivery means 4.

  Specifically, the equilibrium state (M + S⇔M−S; M = sample adsorption site, S = water molecule) of the original water molecules adsorbed and desorbed in the sample 2 reaching infinite time in the sealed space R for each humidity. Exists.

  For example, when the humidity gas is introduced into the sealed space R while the humidity of the humidity gas is continuously changed in the chamber portion 3a, the adsorption / desorption of water molecules in the sample 2 is measured in real time. If the flow rate of the humidity control gas to be introduced (gas flow rate) is too high, the desorption of water molecules from the sample 2 is promoted too much. Conversely, if the flow rate of the humidity control gas to be introduced is too low, There is a problem that the adsorption / desorption reaction of water molecules is hindered by the flow rate of the humidity control gas, such as insufficient adsorption.

  Therefore, when the humidity control gas is introduced into the sealed space R, the humidity control gas is adjusted with a gas flow rate within a range in which the adsorption / desorption of water molecules with respect to the sample 2 approaches the original equilibrium state of the water molecules at the humidity of the humidity control gas. It is preferable to introduce, and as one of the means for that purpose, it is preferable to adjust the gas flow rate and the volume of the chamber part 3a (= volume of the sealed space R).

  Note that whether or not the volume of the chamber portion 3a is appropriate in relation to the flow rate of the humidity control gas is determined by actually introducing the humidity control gas having a predetermined humidity against the sample 2 while introducing it. The adsorption / desorption of water molecules 2 can be determined by performing RifS measurement described later and examining whether the adsorption / desorption reaction of water molecules is approaching the equilibrium state at the humidity.

  Furthermore, when a series of RIfs measurements performed to obtain a reflectance minimum wavelength (described later) by changing the wavelength of the measurement light in the range of 400 to 800 nm by 1 nm in the RIfS measurement described later, The viewpoint that the humidity control gas in the sealed space R can be changed and set to a desired humidity during the time interval of this group of RIfS measurements (time interval for measuring adsorption / desorption of water molecules to the sample). Therefore, the volume of the chamber portion 3a (sealed space R) is preferably substantially the same as or less than the flow rate of the humidity control gas introduced during the time interval.

  As a specific example of the flow rate of the humidity control gas and the volume of the chamber portion 3a, for example, when the flow rate of the humidity control gas to be supplied is 1 L / second or less, the volume of the chamber portion 3a is formed to be 17.0 mL or less. It is preferable that the closed space has a capacity of 1.5 mL to 3.2 mL.

The shape of the chamber portion 3a is not particularly limited, but as illustrated in the top view in FIG. 6, for example, a rectangular parallelepiped (FIG. 6A), an elliptical cross section (FIG. 6B). A columnar shape with a keyhole shape in the cross section (FIGS. 6C and 6D) and a columnar shape with a substantially perfect circular shape in the cross section (FIG. 6E). Among these, it is preferable that the cross section is formed in a substantially circular cylindrical shape (FIG. 6E) or a rectangular parallelepiped shape (FIG. 6A), and in particular, the shape of the cross section of the chamber portion 3a. If the humidity control gas is circular, it is preferable in that the humidity control gas is easily dispersed uniformly in the sealed space R when the humidity control gas is blown out and introduced into the sealed space R from the upper center of the sealed space R.
In addition, as shown in FIG. 2, the edge part (refer FIG. 3 (B)) of the chamber part 3a protrudes, and the flexible O-ring 21 made from rubber | gum is attached to this (FIG. 3). (See (A)).

(groove)
FIG. 3A is a perspective view of the sealed space forming member of the first embodiment when the sealed space forming member 3 is viewed from the lower side (lower side in FIG. 1 or 2). FIG. 3B shows an exploded perspective view of the sealed space forming member 3 of the first embodiment. FIG. 3C shows a view of the sealed space forming member 3 of FIG. 3A taken along the line AA and viewed in the arrow direction. FIG. 4D is a cross-sectional view taken along the lines BB and CC in FIG. 3B and viewed in the arrow direction. In FIG. 3, illustration of the fixing member of the sealed space forming member 3 is omitted.

  As shown in FIG. 3D, a groove 11 having a C-shaped cross section is formed on the upper wall of the chamber portion 3a (the bottom wall of the chamber portion 3a in FIG. 3D). The groove 11 is continuously formed in the gas introduction paths 12A and 12B described above. As shown in FIGS. 3A to 3D, the groove 11 is formed with respect to the C-shaped groove 11 and the gas introduction paths 12A and 12B. Thus, the gas guide member 13 can be penetrated. Further, with this configuration, the gas guide member 13 can be provided without substantially affecting the volume of the chamber portion 3a of the sealed space forming member 3 described above.

(Gas introduction path)
The gas introduction paths 12A and 12B are flow paths for supplying humidity-controlled gas with adjusted humidity and the like to the sealed space R. As illustrated in FIGS. 1 and 2, the inside and the outside of the sealed space R are connected to each other. It is formed so as to communicate. The cross-sectional shapes of the gas introduction paths 12A and 12B are circular, and the diameter of the circle is set to be substantially the same as the outer diameter of the gas guide member 13 described above. Moreover, the opening of the upstream end of gas introduction path 12A, 12B is connected with the humidity control gas delivery means 4 and 4 via the pipe | tube (refer FIG. 1 and FIG. 2).

(Gas guide member)
As shown in FIGS. 2 to 3, the gas guide member 13 is formed in an elongated shape, and a gas inlet 13 a is formed on the peripheral wall thereof. When the gas guide member 13 is inserted into the groove 11 described above and rotated around its axis in the groove 11, the gas inlet 13 a faces the chamber portion 3 a, the gas inlet 13 a becomes the measurement region. Humidity adjustment gas can be introduced so as to be sprayed from a position facing 2a.

  The gas guide member 13 is preferably made of resin from the viewpoint that the gas introduction port 13a can be easily formed. Moreover, it is preferable that the gas guide member 13 has flexibility. As a result, as shown in FIGS. 2A (A) and 2 (B), the gas guide member 13 can be easily inserted while being deformed with respect to the groove 11 and the gas introduction paths 12A and 12B. Further, if the gas guide member 13 is flexible, the gas guide member 13 is simply rotated around its axis in a state of being inserted into the gas introduction paths 12A and 12B and the groove 11, and introduced from the gas introduction port 13a. It is easy to define the direction of humidity control gas. The shapes of the groove 11 and the gas guide member 13 having a C-shaped cross section are not limited to the C-shaped cross section, and may be, for example, a rectangular cross section.

  In addition, you may form continuously the gas guide part (not shown) which has the gas introduction port 13a similar to the gas guide member 13 in gas introduction path 12A, 12B, without providing the gas guide member 13 mentioned above.

(Gas inlet)
The shape of the gas inlet 13a of the gas guide member 13 is not limited to the circular shape of the example shown in FIG. 3, and may be other shapes. For example, as shown in FIGS. 7A and 7C, a plurality of gas inlets 13a may be formed at predetermined intervals. In this case, the plurality of gas inlets 13a,... Need to be formed so that the humidity control gas is blown onto the measurement region from a position facing the measurement region 2a. The position facing the measurement region 2a is, for example, a plane parallel to the substrate when the measurement region 2a is formed on the sensor chip substrate, typically the ceiling of the chamber portion 3a.

  Further, as shown in FIG. 7B, a ring member 13b for adjusting the introduction direction of the humidity control gas may be provided at the center of the gas introduction port 13a. Further, the shape of the gas inlet 13a may be an ellipse (FIG. 7D), a rectangle (FIGS. 7E and 7G), or a rectangle with a different width (FIG. 7F).

  As described above, by adopting the shape and the combination of the gas inlet 13a as described above, the flow of the humidity control gas blown from the gas inlet 13a to the measurement region 2a can be adsorbed and desorbed from the viewpoint of fluid engineering. The gas flow rate can be easily controlled.

The dimension of the gas inlet 13a is preferably 3 mm × 0.5 mm to 3 mm × 25 mm. Therefore, the opening area of the gas inlet 13a becomes preferable is 1.5mm ² ~75mm ^2.

The total area of the gas inlets 13a,... Is defined by the relationship with the gas flow rate. For example, when the gas flow rate is set to 17 mL / second or less, the humidity control gas fluid is supplied to the gas introduction path 12A. , set the speed when introduced into the enclosed space R through the gas inlet port 13a from 12B when moving at 1700 mm / sec, the gas inlet port 13a, the total opening area of ... in 1 mm ² or more Will be. The total opening area of the gas inlets 13a,... Depends on the area of the measurement region 2a, and may be determined based on the area. Here, the ratio of the total opening area of the gas inlets 13a,...: The area of the measurement region 2a is preferably 50: 1 to 480: 1.

(Angle between the introduction direction of the humidity control gas and the measurement surface)
The plane part of the sample 2 in the measurement region 2a in the flow direction of the humidity control gas flowing into the sealed space R due to the shape of the gas introduction port 13a (see the arrow in the alternate long and short dash line) (or the sample is an ecological sample and there is no plane part In this case, the angle (θ) with respect to the planar portion of the substrate or the like that fixes the substrate may be an angle at which the humidity control gas is blown against the planar portion of the sample 2 in the measurement region 2a. It is 70 ° to 110 °, more preferably 85 ° to 95 °, and most preferably 90 ° (see FIG. 4).

(Distance between gas inlet and measurement area 2a)
The distance between the gas inlet and the measurement region 2a may be a distance that allows the humidity-controlled gas introduced into the sealed space R to be sprayed onto the measurement region, and is preferably 1.5 mm to 5 mm.

(Gas discharge passage)
As shown in FIG. 2, the gas discharge paths 14 </ b> A and 14 </ b> B are formed on the inner wall of the chamber portion 3 a of the sealed space forming member 3 so that the sealed space R communicates with the outside. The humidity control gas introduced into the sealed space R is discharged out of the sealed space R through the gas discharge paths 14A and 14B. The gas discharge paths 14A and 14B are connected to a gas discharge mechanism (not shown), and the gas discharge paths 14A and 14B are formed so as to be discharged at a predetermined gas flow rate (for example, 17 mL / second or less). Then, the gas introduction paths 12A and 12B and the gas discharge paths 14A and 14B are substantially closed by the humidity control gas delivery means 4 and 4 and the gas discharge mechanism, and thus are formed in the chamber portion 3a. The space R is sealed and becomes a sealed space. Moreover, the opening area of the openings of the gas discharge passages 14A and 14B is substantially the same as the total opening area of the gas inlets 13a,. Is preferred. Reference numeral 5 denotes a temperature / humidity sensor that is provided in the gas discharge path and measures the temperature and humidity in the sealed space R.

(Fixed part for installing first and second optical fibers)
As shown in FIGS. 2 and 3, an opening 3 b as a fixing portion for installing the first and second optical fibers 6 and 7 is provided on the upper wall portion of the chamber portion 3 a of the sealed space forming member 3. The opening 3b is formed at a position coincident with the measurement region 2a when the sealed space forming member 3 joined to the sensor chip 1 is viewed from above (upper side in FIG. 2). As a result, the measurement light guided from the light source 8 through the first optical fiber 6 is emitted toward the measurement region 2a, and the reflected light reflected by the measurement region 2a is incident on the second optical fiber 7 and enters the spectroscope 9. It is comprised so that it may be guided.

<Sensor chip>
As shown in FIG. 2, the sensor chip 1 includes a substrate 15, an optical thin film 16 formed thereon, and a thin film of the sample 2. Here, the optical thin film 16 may not be provided, and a cover member 17 as shown in FIG. 5 may be provided.

(substrate)
When the measurement light is reflected from the bottom surface by the substrate 15, reflected light is generated. The substrate 15 of the sensor chip 1 may be configured so that the reflected light has a wavelength of 400 nm to 800 nm.

  As the material of the substrate 15, a known material (silicon, silicon wafer or the like) that can fix the optical thin film 16 or the sample 2 for each type of the optical thin film 16 or the sample 2 is used. When the thin film of the sample 2 is formed, the material of the substrate 15 is preferable in that a polymer (PS, PMMA, PC, COP, etc.) can be easily processed into a flat plate shape. When the sample 2 is a biomaterial (cells, proteins, DNA, etc.), the sample is discontinuous and has a high degree of discreteness, making it difficult to form a thin film of the sample 2. Therefore, a DNA microarray for fixing the sample 2 to a spot to be described later Glass substrates for protein chips and acrylic resins are suitable.

(Optical thin film)
The optical thin film 16 of the sensor chip 1 is for adjusting the wavelengths of the measurement light and the reflected light reflected from the bottom surface, and one that can transmit each measurement light and the reflected light reflected from the bottom surface is used. For example, SiN, SiO ₂ , TiO ₂ , TiO ₅ or the like can be used as the optical thin film 16. The thickness of the optical thin film 16 should just be the thickness which adjusts the wavelength of the light after passing the optical thin film 16 to 400 nm-800 nm which a reflectance minimum wavelength can take, for example, if it is SiN, the thickness of the optical thin film 16 will be sufficient as it. The thickness is 45 nm to 90 nm. The optical thin film 16 can be formed on the substrate 15 by a known method such as vapor deposition.

  Here, the “reflectance minimum wavelength” used in the present application will be described. First, for example, as shown in FIGS. 2 and 9, when the measurement light is incident on the substrate 15 and the optical thin film 16 through the first optical fiber 6 by emitting the light source 8, surface reflection (thick broken line) is generated. Each reflected light that is reflected from the bottom surface (thin broken line) is obtained, and a synthesized light is obtained as the reflected light (see FIGS. 9A and 9E). Here, if the wavelength of the incident measurement light is changed, the phase of the wavelength of each reflected light reflected from the surface and the bottom is shifted, and depending on the phase, the wavelengths of the light reflected from the surface and the light reflected from the bottom cancel each other. In combination, there is a wavelength at which the reflectance is minimized. This wavelength is the “reflectance minimum wavelength” (see FIG. 9C). This “reflectance minimum wavelength” also changes depending on the film thickness (FIG. 9C). In addition, the reflectance minimum wavelength also changes when the film thickness of the sensor chip 1 changes due to the mounting of the sample 2 or the adsorption / desorption of water molecules on the sample 2. The adsorption / desorption of water molecules can be measured (see FIGS. 9B, 9D, and 9F).

(sample)
The sample 2 may be any material that can measure the adsorption / desorption of water molecules by the RIfS system 100, and is in a solid phase or liquid phase state. The sample 2 is formed on part or all of the surface of the substrate 15 or the optical thin film 16 to which the measurement light is irradiated (see FIG. 1 and the like). Hereinafter, the region where the sample 2 is formed is referred to as a measurement region 2a.

Examples of the sample 2 may be any sample that is a measurement target of water molecule adsorption / desorption, such as a hydrophobic polymer (polystyrene, polymethyl methacrylate, etc.), a hydrophilic polymer (polyhydrophilic polymer by plasma treatment or the like). Methyl methacrylate, etc.), water-soluble polymers, biomaterials (proteins, phospholipids, nucleic acids, sugar chains, cells, cell membrane fractions, skin, biological secretory components, etc.), surface treatment agents (fluorinated water repellent treatment agents, Hydrophilic surface modifiers, etc.), paints (inks, paints, etc.) and functional materials, but also inorganic compounds. A thin film (layer) itself made of a substance capable of adsorbing water molecules such as SiO ₂ , Si, SiN, ZnO, TiO ₂ (which changes the optical path length) may be used as the sample thin film. Further, it may be in the form of fine particles (colloidal silica, pigment, toner, etc.) or a monomolecular compound (silane coupling agent forming film, LB film forming film, deposited material, etc.).

  When the sample 2 is formed as a thin film, the film thickness may be any thickness as long as the reflectance minimum wavelength can be measured, and is preferably 1 nm to 100 μm, more preferably 10 nm to 1 μm, and still more preferably 10 nm to 700 nm. .

  As a method for forming the thin film of Sample 2, known film formation such as various coatings such as dip coating, spin coating and spray coating, cast manufacturing method, chemical vapor deposition method (CVD), physical vapor deposition method (PVD) and the like. Can be done by the method. When the sample 2 is a discontinuous and discrete biomaterial such as DNA, protein, or cell, it is difficult to form a thin film. For example, the surface of the optical thin film 16 or the substrate 15 is made of polyethylene glycol (PEG). It may be modified with lipid (for example, Biocompatible anchor for membrane: BAM), and biomaterials such as DNA, protein, cells, etc. may be spot-fixed to the modified compound.

(Cover member)
As shown in FIGS. 5A and 5B, the sensor chip 1 may further include a cover member 17 that masks a surface portion of the sample 2 other than the measurement region 2a. The cover member 17 is formed of a known material having a lower hydrophilicity than the sample 2 and is, for example, a hydrophobic polymer (PMMA, PET, PP) or the like. This cover member 17 is advantageous in that the humidity control gas can be prevented from unnecessarily adhering to the thin film or the like of the sample 2 other than the measurement region 2a, and the reduction of water molecule resources can be prevented. . In the example shown in FIG. 5, the cover member 17 covers the thin film of the sample 2 except for the measurement region 2a. For example, the chamber member 3a further prevents water molecules from adsorbing to the surface of the chamber member 3a. It is good also as what covers the inner surface.

<Humidity gas delivery means>
As shown in FIG. 1 and FIG. 2, the humidity control gas delivery means 4 is connected to the openings at the upstream ends of the gas introduction paths 12A and 12B of the sealed space forming member 3, and the humidity etc. are supplied to the gas introduction paths 12A and 12B. This is for delivering adjusted gas, and has a temperature / humidity adjustment unit (not shown). In the RIfS measurement, for example, the humidity gas is sent to the sealed space R and the humidity of the humidity gas is continuously changed to measure the adsorption / desorption of water molecules in the sample 2 in real time. The humidity control gas delivery means 4 preferably has a function of continuously changing the humidity and the like.

<Exhaust mechanism>
The exhaust mechanism (not shown) is a mechanism that is connected to the downstream openings of the gas discharge paths 14A and 14B, has an exhaust fan, for example, and discharges the humidity-controlled gas in the sealed space R. What is necessary is just to have the exhaust capability which can maintain the flow volume (for example, the flow volume of 1 L / min or less in the below-mentioned Example) required in order to measure the adsorption / desorption of the water molecule of the sample 2 in real time.

<Humidity sensor>
The temperature / humidity sensor 5 is a sensor that measures the temperature and humidity of the humidity control gas that stays in the sealed space R, and is provided at a position that does not adversely affect the adsorption / desorption of water molecules with respect to the sample 2 in the RIfS measurement. For example, it is preferable to provide the gas discharge passage as shown in FIG. The temperature / humidity sensor 5 is connected to the control means 10 described later, and is configured to always monitor the humidity and temperature of the sealed space R.

<First and second optical fibers>
The first and second optical fibers 6 and 7 are each constituted by a bundle of a plurality of fine optical fibers. As shown in FIGS. 1 and 2, each of the first optical fiber 6 and the second optical fiber 7 is provided. A measurement probe is formed by one end, and is inserted and fixed in the opening 3b of the sealed space forming member 3 so that the measurement probe faces the measurement region 2a in the sealed space R. The other end of the first optical fiber 6 is disposed at the irradiation position of the light source 8, and the other end of the second optical fiber 7 is connected to the spectrometer 9. When the light source 8 is turned on, measurement light having a predetermined wavelength is emitted from one end of the first optical fiber 6 and reflected by the measurement region 2a or the like (see FIG. 9B), and the reflected light is reflected on the second optical fiber 7 from one end. In order to make it enter into the inside, the 1st optical fiber 6 should just be able to guide the measurement light from the light source 8, and the 2nd optical fiber 7 can guide the light of the wavelength (400 nm-800 nm) mentioned above.

<Control means>
The control means 10 has a storage means (not shown), and this storage means stores a program for controlling each device described above and measuring the adsorption / desorption of water molecules by the RIfS measurement described later. .

<< RIfS measurement >>
Hereinafter, a method (water molecule adsorption / desorption measurement method) of measuring water molecule adsorption / desorption by RIfS measurement by the RIfS system 100 having the sealed space forming member 3 of the first embodiment will be described.

  The method for measuring adsorption / desorption of water molecules according to the present invention includes a humidity control step of adjusting the humidity of the humidity control gas to be introduced into the sealed space R to the humidity of the measurement conditions, and the measurement of the sealed space R formed by the chamber portion 3a. A gas introduction step of introducing the adjusted humidity gas into the region 2a and a measurement step of measuring the amount of water molecules in the sample 2 by RIfs.

[Humidity control process]
As shown in FIG. 10, the humidity adjustment process includes a primary humidity adjustment process S <b> 1-1 and secondary to n-th humidity adjustment processes S <b> 1-3. Among these, the second to n-th humidity control steps S1-3 are performed in parallel with the gas introduction step S1-4. Here, “n” is the total number of stages when the humidity of the humidity control gas introduced into the sealed space R is changed stepwise by the RIfS system 100. “I” indicates what level of humidity adjustment is currently performed among all stages of humidity adjustment.

  For example, when the humidity of the humidity control gas introduced in stages at an increasing rate of + 1% humidity / min is changed from 20% to 22%, the air conditioning space R is adjusted to a predetermined humidity (for example, 21%). One minute of moistening is the primary humidity conditioning step. In this specific example, n = 3, i = 1 to 3, humidity is adjusted to 20% when i = 1, humidity is 21% when i = 2, and humidity is adjusted to 22% when i = 3. become. About the variation | change_quantity of the humidity in 1 step, it is 0.1-10RH% normally, Preferably it is 0.5-5RH%.

  In step S1-1, the humidity of the humidity control gas is adjusted to the humidity set in the first humidity control stage. In the above specific example, the humidity of the humidity control gas is adjusted to 20% by the humidity control gas delivery means 4 by the temperature / humidity adjustment unit (not shown) of the control means 10.

In step S1-2, i = 2 is set, and the number (n) of the measurement steps described above is set. In the specific example described above, the measurement stage is humidity 20-22%, so n = 3.
In step S1-3, the i-th (i-th stage) humidity control is performed. When i = 2, in the above specific example, the humidity control gas to be introduced is set to a humidity of 21%.

[Gas introduction process]
In the gas introduction process (step S1-4), the humidity-controlled gas conditioned in the (i-1) th humidity control process is opposed to the gas introduction port 13a of the sealed space forming member 3 (the measurement area 2a of the sealed space R). Is a step of introducing the humidity control gas whose humidity has been adjusted from the measurement area 2a. In this gas introduction step, an i-th humidity adjustment step (S1-3), an irradiation step (S1-5), and a measurement (S1-6) described later are performed in parallel (see FIG. 10).

  As described above, the flow rate of the humidity control gas introduced into the sealed space R is within the range in which the adsorption / desorption of water molecules with respect to the sample 2 approaches the equilibrium state of the above-described original adsorption / desorption of water molecules at the humidity of the humidity control gas. A gas flow rate is preferred. That is, the capacity of the sealed space R is approximately equal to or less than the amount of the humidity control gas supplied to the sealed space during the time interval for measuring adsorption / desorption of water molecules to the sample. It is preferable to be formed. As a specific example, the time interval for measuring the adsorption / desorption of water molecules with respect to the sample by RIfS (the film thickness d of the sample reflecting it) is 1 second and is formed by the chamber portion 3a of the sealed space forming member 3 or the like. When the volume of the enclosed space R is 17.0 mL or less, the flow rate of the humidity control gas to be supplied is preferably 1 L / min (about 16.7 mL / sec) or less.

  The flow direction of the humidity control gas introduced into the sealed space R from the gas introduction port 13a in the gas introduction step may be a direction in which the humidity control gas is blown against the sample 2. Preferably, the planar measurement region is a thin film of the sample 2 In the case where 2a or the sample 2 is a biomaterial such as protein and is discontinuous, the angle (θ) with respect to the flat surface on which the biomaterial is fixed is 70 ° or more and 110 ° or less.

[Irradiation process]
In the irradiation step (step S1-5), as shown in FIG. 9B, the measurement light is incident on the measurement region 2a and the reflected light is continuously received. The irradiation process is performed in parallel with other processes as shown in FIG. Specifically, the light source 8 that emits light of a predetermined wavelength as the measurement light is turned on, and the measurement light is continuously incident on the measurement region 2a of the sealed space R through the first optical fiber 6, and obtained while being incident. The reflected light is received by the first optical fiber 7 and continuously guided to the spectrometer 9.

[Measurement process]
As shown in FIG. 2, the measurement process (step S1-6) is a process of measuring the amount of water molecules in the sample 2 by performing RIfS measurement based on the received light data when light is received in the irradiation process. As described above, since the gas introduction process is performed in parallel during the measurement process, the humidity in the sealed space R is constantly adjusted, and the humidity is changed or substantially maintained over time.

  In the measurement process, RifS measurement is performed at predetermined time intervals (for example, 20 milliseconds) while continuously adjusting the humidity of the sealed space R as described above. When the light source 8 is a white light source, the RIfS measurement is performed a plurality of times so as to cover 400 nm to 800 nm while sequentially changing the wavelength detected on the spectroscope 9 side. For example, RIFS measurement is performed while sequentially changing the wavelength to be detected by 1 nm in a peripheral wavelength region (for example, a wavelength of 500 to 550 nm) with a minimum reflectance wavelength. In this case, the measurement is performed 50 times within the range of 50 nm in the above example. When one RIfS measurement is performed in 20 milliseconds, 50 RIfS measurements in one group take 50 RIfS measurements × 20 milliseconds / times RIfS measurement = 1000 milliseconds (1 second).

  In step S1-6, arbitrarily, as shown in FIG. 11, the thickness change (Δd [nm]) of the sample 2 measured at each time point of RIfs measurement (for example, t1 to t4 in FIG. 11) is calculated, The change rate of Δd at each time point (in the example of FIG. 11, the slope at each time point in the graph: see the arrow) is obtained, and whether the slope of Δd (change in reflectance) is close to 0 (for example, 0.3 or less). May be examined. If the slope of Δd (reflectance change) is close to 0, it can be determined that the state has substantially shifted to the equilibrium state of water adsorption / desorption, and if not, it can be determined that the transition is in progress. Note that the humidity shown on the right side of FIG. 11 indicates the humidity of the humidity control gas introduced into the sealed space R.

  In step S1-7, it is determined whether or not the humidity control process up to the i-th order is completed (whether n <i). For example, when measuring the adsorption / desorption of water molecules at a humidity of 20 → 22%, it is judged whether or not the humidity adjustment process is completed up to 22%. If YES, the series of measurements is completed and completed. If it is not and it is NO, after incrementing n by step S1-8, it will return before step S1-3 and will transfer to the following humidity control process.

(Operation / Effect of Embodiment 1)
Hereinafter, operations and effects when the RIfS measurement is performed by the RIfS system 100 using the sealed space forming member 3 of the first embodiment will be described.

  (1) The sealed space forming member 3 of the first embodiment is a sealed space forming member for use in the RIfS system 100 to form a sealed space R that encloses the sample 2. As shown in FIG. There is a gas inlet 13a for introducing the humidity control gas into the sealed space R so as to blow the humidity control gas from the position opposite to the measurement region 2a of the sample 2.

  Therefore, if the humidity control gas is introduced to the measurement region 2a by the RIfS system 100 having the sealed space forming member 3, the humidity control gas is introduced so as to be blown against the measurement region 2a. The problem of introducing the humidity control gas into the small volume sealed space R by the path, that is, the gas is introduced into the measurement region 2a at a gas flow rate higher than that of the constant temperature bath, Although the adsorption of water molecules occurs due to the introduction, the desorption of water molecules is also promoted, and there is a problem that it is difficult to reproduce the original adsorption / desorption of water molecules, that is, a predetermined gas flow rate (for example, 1 L / min or less). ), It is difficult to make a transition to the equilibrium state of adsorption / desorption of water molecules with respect to the sample even when the gas is introduced into the measurement region 2a. It can be a RIfS measured in a manner reflecting the desorption for water molecules of the sample.

  (2) The sealed space R has a capacity substantially equal to or less than the amount of the humidity control gas supplied to the sealed space R during the time interval for measuring adsorption / desorption of water molecules to the sample. Therefore, water molecules are supplied to the measurement region 2a without deficiency in the sealed space R in the chamber portion 3a, and the humidity control gas spreads uniformly in the sealed space R. Time until it becomes uniform can be reduced as much as possible.

  (3) If the ratio of the total opening area of the gas introduction port 13a of the sealed space forming member 3: the area of the measurement region 2a is 50: 1 to 480: 1, the gas introduction port 13a is connected to the measurement region 2a. Humidity control gas can be sprayed suitably.

  (4) The gas introduction port 13a is provided so that the humidity control gas is in a range of 70 ° to 110 ° with respect to the plane of the measurement region 2a. The effect (1) can be preferably obtained. Furthermore, if the angle (θ) is 85 ° to 95 °, the effect of (1) can be more suitably obtained.

  (5) A plurality of gas inlets 13a are provided, and each opening of the gas inlets 13a,... Is at least one of a circle, an ellipse, and a rectangle. A shape suitable for introducing gas into the measurement region 2a can be obtained. Here, whether or not the shape of the gas inlet 13a is suitable for introduction of humidity control gas is determined by changing the shape of the gas inlet 13a to various shapes and measuring the adsorption / desorption of water molecules by the above-described RIfS measurement. By doing so, it can be determined by whether the adsorption / desorption of water molecules is fast or slow in approaching the equilibrium state.

  (6) It is provided with a separate gas guide member 13 for adjusting the angle (θ) at which the gas flow of the humidity control gas introduced into the sealed space R from the gas introduction port 13a is supplied to the measurement region 2a. Thus, the gas guide member 13 can be processed and formed to form the desired gas inlet 13a.

  Further, if the gas guide member 13 has a cylindrical shape and is inserted in the groove 11 of the sealed space forming member 3 as described above, the gas guide member 13 is rotated around its axis, for example. Since the installation state can be changed, the direction in which the humidity control gas is introduced into the sealed space R, that is, the angle (θ) can be easily changed as intended by the user. Therefore, the adjustment of the introduction direction of the humidity control gas described above becomes easy. Further, since the gas guide member 13 is a separate body, there is an advantage that maintenance is easy.

  (7) The surface forming the sealed space R other than the measurement region 2a (the portion other than the measurement region 2a of the thin film of the sample 2, the inner surface of the chamber portion 3a, etc.) is covered with the cover member 17 that is more hydrophobic than the sample 2 If it is, the adsorption / desorption of water molecules to the portion other than the measurement region 2a can be suppressed, and the amount (resource) of free water molecules in the sealed space R can be ensured as much as possible.

  As described above, since more free water molecules are secured in the sealed space R, the water molecules are adsorbed and desorbed when the humidity control gas is introduced into the sealed space R as compared with the case where the cover member 17 is not provided. Is easily transitioned to an equilibrium state.

[Embodiment 2]
7A and 8A show a sealed space forming member 3A of the RIfS measurement system 100A according to the second embodiment. In addition, about the one part member etc. which are common in the RIfS measurement system 100 of Embodiment 1, the same code | symbol is attached | subjected or illustration is abbreviate | omitted and the description is abbreviate | omitted.

  The sealed space forming member 3A according to the third embodiment includes a chamber portion 3a, a groove 11 having a C-shaped cross section, gas introduction paths 12A and 12B, and a gas guide member 13 provided in the groove 11 and the gas introduction path 12A. And a gas discharge path 14B.

  In the sealed space forming member 3A of the second embodiment, one end portions of the first and second optical fibers 6 and 7 extend above the measurement region 2a of the sealed space R from the position of the chamber portion 3a adjacent to the gas introduction port 13a. Has been drooped to do.

(Operation / Effect of Embodiment 2)
According to the RIfS measurement system 100A using the sealed space forming member 3A of Embodiment 2, the sealed space R is formed in a rectangular parallelepiped shape, and the opening of the gas discharge path 14B is formed on the inner wall surface of the chamber portion 3a. It is easy to specify the discharge amount when the humidity control gas in the sealed space R is discharged. In addition, the humidity control gas introduced by the first and second optical fibers 6 and 7 is guided to the measurement region 2a.

[Embodiment 3]
FIG. 8B shows a sealed space forming member 3B of the RIfS measurement system 100B according to the third embodiment. In addition, about the one part member etc. which are common in the RIfS measurement system 100 of Embodiment 1, the same code | symbol is attached | subjected or illustration is abbreviate | omitted and the description is abbreviate | omitted.

  The sealed space forming member 3B according to the third embodiment includes a chamber portion 3a, a groove 11 having a U-shaped cross section, gas introduction paths 12A and 12B, and a gas guide member 13 provided in the groove 11 and the gas introduction path 12A. And a gas discharge path 14B.

  In the sealed space forming member 3B of the third embodiment, as shown in FIG. 8B, a gas guide member 13 is inserted into the gas introduction paths 12A and 12B and the groove 11. And the opening 3b is each formed in the bottom part of the gas guide member 13 and the groove | channel 11 in the position which corresponds to each position of the measurement area | region 2a and the gas inlet 13a by planar view. The probes at the ends of the first and second optical fibers 6 and 7 are positioned above the measurement region 2a of the sealed space R in the chamber portion 3a through the opening 3b and the gas inlet 13a. It is drooping.

(Operation / Effect of Embodiment 3)
According to the RIfS measurement system 100B using the sealed space forming member 3 of the third embodiment, the first and second optical fibers 6 and 7 are configured as described above and are originally passed through the gas introduction port 13a for blowing out the humidity control gas. Since it hangs down, the first and second optical fibers 6 and 7 can be installed without obstructing the flow of the humidity control gas, and the first and second optical fibers 6 and 7 are supplied to the measurement region 2a. This also serves as a guide when the gas is sprayed, and the humidity control gas is preferably sprayed onto the measurement region 2a.

[Embodiment 4]
FIG. 8C shows a sealed space forming member 3C of the RIfS measurement system 100C according to the fourth embodiment. In addition, about the one part member etc. which are common in RIFS measurement system 100B of Embodiment 3, the same code | symbol is attached | subjected or illustration is abbreviate | omitted and the description is abbreviate | omitted.

  The sealed space forming member 3C of the fourth embodiment includes a chamber portion 3a, a groove 11 having a U-shaped cross section, gas introduction paths 12A and 12B, a gas discharge path 14B, a U-shaped groove 11 and a gas introduction path 12A. , 12B and the gas guide member 13 and the like penetrated. Further, the space inside the gas guide member 13 and the inside of the chamber portion 3a are formed in a columnar shape centered on the measurement region 2a.

(Operation / Effect of Embodiment 4)
According to the RIfS measurement system 100C using the sealed space forming member 3C of the fourth embodiment, the inside of the gas guide member 13 has a cylindrical shape. 13 is easily circulated and uniform in the humidity control gas.

  Furthermore, since the position of the gas inlet 13a is the center of the columnar shape, the humidity-controlled gas that is well mixed inside the gas guide member 13 is blown out into the sealed space R. Since the sealed space R in the chamber portion 3a is also formed in a cylindrical shape, the humidity control gas introduced so as to be blown to the measurement region 2a from a position facing the measurement region 2a is convection in the sealed space R. Then, when it flows so as to blow again against the measurement region 2a (see the black arrow in FIG. 8C), the convection moving distance of the humidity control gas is uniform, so that the mixing unevenness of the humidity control gas also occurs in the chamber portion 3a. The humidity control gas can be suitably blown onto the measurement region 2a while improving the above.

  Here, the inner peripheral wall of the chamber portion 3a is formed so as to extend vertically in the vertical direction, but the direction of the humidity control gas flowing so as to blow again against the measurement region 2a is relative to the plane portion of the measurement region 2a. The angle (θ) may be formed in a barrel shape so as to be in a range of 70 ° to 110 °.

[Embodiment 5]
FIG. 8D shows a sealed space forming member 3C of the RIfS measurement system 100D according to the fifth embodiment. In addition, about the one part member etc. which are common in the RIfS measurement system 100 of Embodiment 1, the same code | symbol is attached | subjected or illustration is abbreviate | omitted and the description is abbreviate | omitted.

  The sealed space forming member 3D of the fifth embodiment penetrates the chamber portion 3a, the groove 11 having a U-shaped cross section, the gas introduction paths 12A and 12B, the gas discharge path 14B, the groove 11 and the gas introduction paths 12A and 12B. The gas guide member 13 and the like are mounted. The 1st, 2nd optical fibers 6 and 7 are arrange | positioned according to the direction through which humidity-control gas flows so that it may protrude in the sealed space R from the position a little outside from the edge of the gas inlet 13a. The sealed space forming member 3D is formed so that the sealed space R inside the chamber portion 3a is substantially cylindrical with the measurement region 2a as the center.

(Operation / Effect of Embodiment 5)
According to the RIfS measurement system 100D using the sealed space forming member 3D of the fifth embodiment, the first and second optical fibers 6 and 7 blow out from the gas inlet 13a to the sealed space R as shown in FIG. 8D. While guiding the flow of the humidity control gas, it plays a role of suppressing the movement of the humidity control gas introduced into the sealed space R to the side, particularly in the direction toward the gas discharge path 14B. Therefore, the effect at the time of the convection of Embodiment 4 mentioned above can be improved, and humidity control gas can be sprayed to the measurement area | region 2a more suitably.

[Embodiment 6]
FIG. 8E shows a sealed space forming member 3E of the RIfS measurement system 100E according to the sixth embodiment. In addition, about the one part member etc. which are common in RIFS measurement system 100B of Embodiment 3, the same code | symbol is attached | subjected or illustration is abbreviate | omitted and the description is abbreviate | omitted.

  The sealed space forming member 3E of the sixth embodiment penetrates the chamber 3a, the groove 11 having a U-shaped cross section, the gas introduction paths 12A and 12B, the gas discharge path 14B, the groove 11 and the gas introduction paths 12A and 12B. The gas guide member 13 and the like are mounted.

  In the sealed space forming member 3E of the sixth embodiment, a wall 3c extending from the ceiling of the chamber 3a on the side of the gas inlet 13a to the vicinity of the lower measurement region 2a is formed. A gap is formed between the lower end of 3b and the sensor chip 1 (see FIG. 8E). The wall 3b divides the sealed space R in the chamber 3a into almost two spaces, and a discharge path 14B is formed in one of the spaces (on the right side in FIG. 8E).

(Operation / Effect of Embodiment 6)
Since the above-described wall 3b extends to the upper vicinity in the vicinity of the measurement region 2a, the humidity control gas introduced toward the measurement region 2a along the wall 3b is guided and substantially perpendicular to the measurement region 2a. Will be sprayed at an angle (θ) ≈90 °. In addition, the above-described convection effect is further enhanced. Further, since this extending wall 3b partitions the sealed space R in the chamber 3a into almost two spaces, the amount of gas to be introduced is the left space including the measurement region 2a (FIG. 8E ) Only on the left side). Furthermore, since the gap between the wall 3b and the sensor chip 1 is the only part where the gas blown to the measurement region 2a moves downstream toward the discharge path 14B, the gas flow flowing downstream causes a gap in the measurement region 2a. A partial suction state is generated in the vicinity, and as a result, there is an advantage that the flow of the humidity-controlled gas to be sprayed is promoted.

[Embodiment 7]
FIG. 8F shows a sealed space forming member 3F of the RIfS measurement system 100F of the seventh embodiment. In addition, about the one part member etc. which are common in RIFS measurement system 100B of Embodiment 3, the same code | symbol is attached | subjected or illustration is abbreviate | omitted and the description is abbreviate | omitted.

  The sealed space forming member 3F of the seventh embodiment penetrates the chamber portion 3a, the groove 11 having a U-shaped cross section, the gas introduction paths 12A and 12B, the gas discharge path 14B, the groove 11 and the gas introduction paths 12A and 12B. The gas guide member 13 and the like are mounted. The opening of the gas discharge path 14B is formed in the inner wall of the chamber portion 3a located immediately on the side of the measurement region 2a (the back side in FIG. 8F).

(Operation / Effect of Embodiment 7)
Since the opening of the gas discharge path 14B is formed on the immediate side of the measurement region 2a (the back side in FIG. 8F), in addition to the effect of convection occurring on both sides of the measurement region 2a, When the humidity control gas is discharged from the opening, a partial suction pressure is generated around the measurement region 2a, and the effect of promoting the blowing of the humidity control gas to the measurement region 2a is obtained as in the sixth embodiment. In addition, since the opening is connected to the exhaust mechanism, the strength of the flow of the humidity control gas blown to the measurement region 2a can be made positive or negative by adjusting the exhaust capability of the exhaust mechanism (not shown). Is advantageous in that it can also be controlled.

[Embodiment 8]
FIG. 8G shows the sealed space forming member 3G of the RIfS measurement system 100G of the eighth embodiment. In addition, the same code | symbol is attached | subjected about some members etc. which are common with RIFS measuring system 100F of Embodiment 7, or illustration is abbreviate | omitted and the description is abbreviate | omitted.

  The sealed space forming member 3G of the eighth embodiment penetrates the chamber portion 3a, the groove 11 having a U-shaped cross section, the gas introduction paths 12A and 12B, the gas discharge path 14B, the groove 11 and the gas introduction paths 12A and 12B. The gas guide member 13 and the like are mounted. Furthermore, four openings at the upstream end of the gas discharge path 14B are provided on the chamber 3a on both sides of the measurement region 2a (left and right in FIG. 8 (G)) and the back side and the near side (front and back in FIG. 8 (G)). Each is formed on the inner wall (partially not shown).

(Operation / Effect of Embodiment 8)
The distances from the measurement region 2a to each of the four openings described above are substantially equal, and the humidity control gas is uniformly discharged from the sealed space R through the four openings. As a result, the flow of the humidity control gas blown and discharged to the measurement region 2a becomes uniform, which is advantageous in that humidity unevenness is unlikely to occur between the portions in the sealed space R.

  In Examples 1 to 4 described below, the dimensions of each part of the sealed space forming member of Embodiment 1 are set in detail, and in Examples 5 to 8 the dimensions of each part of the sealed space forming member of Embodiment 2 are set in detail as shown in Table 1 and actually Measurements were made using a RIfS system.

[Example 1]
<< Manufacture of sealed space forming member >>
The sealed space forming member 3 of Example 1 was designed with the following contents, and manufactured by precision processing using a material: polymethyl methacrylate (PMMA) (manufactured by Sumitomo Chemical Co., Ltd.).
・ Dimension of chamber portion 3a: 25.2 mmφ × 3.5 mm (height)
-Volume of chamber part 3a: 1.75 mL
・ Dimensions of gas introduction paths 12A and 12B: φ6.1 mm, length (shortest part) 10.4 mm
・ Dimension of groove 11: φ6.1 mm, arc 3 mm
Gas guide member 13 (material / polyurethane, dimension / outer diameter: φ26 mm, inner diameter: φ4 mm, length 46 mm)
・ Dimension of gas inlet 13a (rectangular): 3 mm × 20 mm
-Opening area of the gas inlet 13a: 60 mm ²
The angle (θ) of the gas inlet 13a for introducing the humidity control gas with respect to the measurement region 2a: 71 °
・ Dimensions of gas discharge paths 14A and 14B: 4 mm (horizontal) * 2 mm (vertical)
・ Dimension of opening 3b: φ2.5 mm, relative distance between opening 3b and gas inlet 13a: 2 mm

<Manufacture of sensor chip>
The sensor chip 1 was manufactured as follows.
A sensor chip (substrate 15: Si / optical thin film 16: SiN, thickness 1 mm / 66 nm) dedicated to “MI-Affinity” is used, and a 5 wt% solution of Fresella R (manufactured by Panasonic Electric Works Co., Ltd.), which is a superhydrophilic material. The sample was prepared and applied to the surface of the sensor chip using a spin coater under the conditions of slope (SL) 5 seconds, 3000 rpm, 60 seconds to produce a sensor chip 1 to be analyzed.

<< RIfS measurement >>
Using the sealed space forming member 3 and the sensor chip 1 manufactured as described above, RIfS measurement was performed by the RIfS system 100 as follows.

(Preparation)
The RIfS system used in the first embodiment includes a control unit 10 (general PC), a RIfS apparatus, a humidity control gas delivery unit 4 and the like.
As the humidity control gas delivery means 4, a small temperature / humidity adjustment device “GenRH-A” (manufactured by Surface Measurement Systems, UK) capable of supplying an appropriate amount of humidity control gas to the flow path was used.

  As the RIfS apparatus, a reflection type RIfS water adsorption / desorption measurement apparatus “MI-Affinity” (registered trademark, Konica Minolta Technology Center Co., Ltd.) was used. This RIfS apparatus includes a commercially available light source 8, first and second optical fibers 6 and 7, a spectrometer 9, a temperature controller 5A, a temperature sensor 5, a temperature sensor 19 for measuring the temperature of the sensor chip 1, and a temperature adjusting means 20. Etc.

  Then, the sealed space forming member 3 and the sensor chip 1 are joined and set in a sensor unit (not shown) of the RIfS apparatus to construct a gas channel (vertical channel A-1) including the sealed space R. (See FIG. 2 etc.). The humidity control gas delivery means 4 and “MI-Affinity” are connected to the gas flow path, and the humidity control gas generated from the humidity control gas delivery means 4 is supplied to the sample 2 (flocser R) in the measurement region 2a. did. The first optical fiber is the outer side (cladding) that emits light from the light source, and the second optical fiber is the inner side (core) that is arranged concentrically with the first optical fiber that returns the reflected light to the spectroscope 9. The first and second optical fibers have a clad / core structure. One end of the composite bundle of the first and second optical fibers 6 and 7 is fixed to the opening 3b so as to be located 1.3 mm above the measurement region 2a, and the projection length of the composite bundle into the sealed space R (2. 2 mm).

(Measurement)
The humidity of the sealed space R was controlled by the humidity control gas delivery means 4 in the following order (1) to (5). Humidity control was performed using dry nitrogen gas, and the flow rate of the humidity control gas to the sealed space R during humidity control was set to 100 mL / min. In addition, in the RIfS measurement, one RIfS measurement was performed in about 20 milliseconds, and 50 RIfS measurements were performed over 1 second as a group of RIfS measurements. The group 1 RIFS measurement was performed at least 3000 times, and the humidity control was performed by installing package software “SpecView” (manufactured by SpecView Corporation, USA) in the control means 10 as a monitor control system (SCADA), The humidity control level was PID controlled according to the program (the following (1) to (5)). The results of Example 1 are shown in Table 1 below and FIG.
(1) A humidity control gas (temperature: 25 ° C., 10 RH% (RH: relative humidity)) is continuously sent to the sealed space R for 15 minutes.
(2) The humidity of the humidity control gas to be sent is changed from 10 RH% to 80 RH% in 30 minutes.
(3) Maintain the humidity of the humidity control gas to be sent at 80 RH% for 15 minutes.
(4) Dehumidification from 80 RH% to 10 RH% of the humidity control gas to be sent is changed in 30 minutes.
(5) Maintain the humidity of the humidity control gas to be sent at 10 RH% for 15 minutes.

[Example 2]
In Example 2, RifS measurement and the like are performed in the same manner as in Example 1 except that the angle (θ) of the gas inlet 13a for introducing the humidity control gas with respect to the measurement region 2a in Example 1 is changed from 71 ° to 56 °. went. The results of Example 2 are shown in Table 1 below and FIG.

[Example 3]
In Example 3, RifS measurement and the like are performed in the same manner as in Example 2 except that the size (rectangular) of the gas inlet 13a is changed from “3 mm × 20 mm” to “3 mm × 3.5 mm” in Example 2. It was. The results of Example 3 are shown in the following [Table 1] and FIG.

[Example 4]
In Example 4, RifS measurement or the like was performed in the same manner as in Example 1 except that the angle (θ) of the gas inlet 13a for introducing the humidity control gas with respect to the measurement region 2a in Example 3 was changed from 56 ° to 45 °. went. The results of Example 4 are shown in Table 1 below and FIG.

[Example 5]
As the sealed space forming member used in Example 5, the sealed space forming member 3A of Embodiment 2 described above was manufactured with the following dimensions, and the RIfS measurement was performed in the same manner as in Example 1. In addition, 3A of sealed space formation members were manufactured using the same * as Example 1. FIG. The results of Example 5 are shown in [Table 1] below.
-Dimensions of chamber part 3a: 27.0 mm x 18.0 mm (vertical, horizontal) x 3.5 mm (height)
-Volume of chamber part 3a: 1.70 mL
・ Dimension of groove 11: φ6.1 mm, arc 3 mm
Gas guide member 13 (material / polyurethane, dimensions / outer diameter: φ26 mm, inner diameter: φ3 mm, length 46 mm)
・ Dimension of gas inlet 13a (rectangular): 3 mm × 20 mm
-Opening area of the gas inlet 13a: 60 mm ²
The angle (θ) of the gas inlet 13a for introducing the humidity control gas with respect to the measurement region 2a: 71 °
・ Dimensions of gas discharge paths 14A and 14B: 4 mm wide × 2 mm vertical • Dimension of opening 3 b: φ2.5 mm,
-Relative position of opening 3b and gas inlet 13a: 2 mm

[Example 6]
In Example 6, RifS measurement and the like were performed in the same manner as in Example 5 except that the angle (θ) of the gas inlet 13a for introducing the humidity control gas with respect to the measurement region 2a in Example 5 was changed from 71 ° to 56 °. went. The results of Example 6 are shown in the following [Table 1] and FIG.

[Example 7]
In Example 7, RifS measurement and the like were performed in the same manner as in Example 6 except that the size (rectangular) of the gas inlet 13a in Example 6 was changed from “3 mm × 20 mm” to “3 mm × 3.5 mm”. It was. The results of Example 7 are shown in the following [Table 1] and FIG. 14 (B).

[Example 8]
In Example 8, RifS measurement and the like were performed in the same manner as in Example 7 except that the angle (θ) of the gas inlet 13a for introducing the humidity control gas with respect to the measurement region 2a in Example 7 was changed from 56 ° to 45 °. went. The results of Example 8 are shown in the following [Table 1] and FIG.

[Comparative Example 1]
In Comparative Example 1, unlike the example, gas introduction was performed to introduce humidity control gas from the side direction to the measurement region. First, the sealed space forming member used in Comparative Example 1 will be described. In addition, the code | symbol is attached | subjected about the component same as the sealed space formation member of Embodiment 1, 2, and the description is abbreviate | omitted.

<< Closed space forming member of Comparative Example 1 >>
As shown in FIG. 12, the sealed space forming member 22 of Comparative Example 1 includes a reaction part 23 for adsorbing and desorbing water and a gas introduction path communicating with the sealed space (reaction chamber) R ′ of the reaction part 23. 22a and a gas discharge path 22b. This reaction part 23 is inserted with a rounded rectangular groove 23a, a gas inlet 23b, a gas outlet 23c, and first and second optical fibers 6 and 7 formed in the plane part of the island inside the groove 23a. An opening (fixing portion) 3b for fixing, an O-ring 24 (see FIG. 12 (A)), etc., which is formed in the same shape thicker than the depth of the groove 23a and is fitted and fixed to the groove 23a. doing. When a sealed space forming member is joined to the sensor chip 1 with the O-ring 24 fitted and fixed in the groove 23a (see FIG. 12E), a sealed space R ′ is formed inside the O-ring 24. (Not shown). The gas introduction port 23b facing the sealed space R ′ communicates with the gas introduction path and is formed at an angle θ with respect to the measurement region 2a. On the other hand, the gas discharge port 23c communicates with the gas discharge path 22b.

<< Manufacture of sealed space forming member >>
The sealed space forming member 22 of Comparative Example 1 was designed with the following contents, and manufactured by precision processing using a material PMMA (manufactured by Sumitomo Chemical Co., Ltd.).
-Dimensions of reaction chamber R ': 16.0 mm x 3.0 mm x 0.1 mm
-Volume of reaction chamber R ': 0.05 mL
・ Dimension of gas inlet 23b: φ1mm
-Opening area of the gas inlet 23b: 0.785 mm ²
The angle (θ) of the gas inlet 23b for introducing the humidity control gas with respect to the measurement region 2a: 11 °
・ Dimension of opening 3b: φ2.5 mm

The sensor chip 1 was manufactured in the same manner as in Example 1. Note that one end of the combined bundle of the first and second optical fibers 6 and 7 is fixed to the opening 3b so as to be located 1.3 mm above the measurement region 2a, and the protruding length of the combined bundle into the reaction chamber R ′ (2.2 mm).
Further, the RIfS measurement was performed in the same manner as in Example 1 except that the humidity control level of Comparative Example 1 was PID controlled according to the following humidity control program ((1) to (5) below). The results of Comparative Example 1 are shown in the following [Table 1] and FIG.
(1) A humidity control gas (temperature: 25 ° C., 10 RH% (RH: relative humidity)) is continuously sent to the sealed space R for 10 minutes.
(2) The humidity of the humidity control gas to be sent is changed from 10 RH% to 80 RH% in 15 minutes.
(3) Maintain the humidity of the humidity control gas to be sent at 80 RH% for 10 minutes.
(4) Dehumidification from 80 RH% to 10 RH% of the humidity control gas to be sent is changed in 15 minutes.
(5) Maintain the humidity of the humidity control gas to be sent at 10 RH% for 10 minutes.

[Comparative Example 2]
In the comparative example 2, the gas introduction which introduces humidity control gas from the side direction to the measurement region 2a was performed by a method different from the example and different from the comparative example 1. First, the sealed space forming member used in Comparative Example 2 will be described. In addition, the code | symbol is attached | subjected about the component same as the sealed space formation member of Embodiment 1, 2, and the description is abbreviate | omitted.

<< Closed space forming member of Comparative Example 2 >>
As shown in FIG. 13, the sealed space forming member 25 of Comparative Example 2 is formed of a recess (chamber portion) 25a formed at the center thereof and a gas introduction path communicating with the chamber portion 25a. 25b and a gas discharge path 25c. The gas introduction path 25b is formed wide and penetrates from the inner wall surface of the chamber portion 25a to the outside. In addition, the gas introduction path 25b penetrates from another inner wall surface of the chamber portion 25a to the outside.

  When a sealed space forming member is joined to the sensor chip 1 with the O-ring 26 attached to the protruding portion of the chamber portion (see FIG. 13E), a sealed space R ″ is formed inside the O-ring 26. The gas introduction port 25ba of the gas introduction passage 25b facing the sealed space R ″ is formed so as to have an angle θ with respect to the measurement region 2a of the sensor chip 1. The angle θ is based on the opening center of the gas inlet 25ba.

<< Manufacture of sealed space forming member >>
The sealed space forming member of Comparative Example 1 was designed with the following contents, and manufactured by precision processing using the material PMMA (manufactured by Sumitomo Chemical Co., Ltd.).
・ Dimension of chamber portion 25a: 26.0 mm × 18.0 mm × 5.0 mm
-Volume of chamber part 25a: 2.34 mL
・ Dimensions of gas introduction path 25b: 3 mmφ, length 8.6 mm
・ Dimension of gas inlet 25ba: 3 mmφ
-Opening area of gas inlet 25ba: 7 mm ²
The angle (θ) of the gas inlet 13a for introducing the humidity control gas with respect to the measurement region 2a: 21 °
・ Dimension of gas outlet: 3 × 9 oblong hole ・ Dimension of opening 3b φ2.5 mm

  The manufacture of the sensor chip and the RIfS measurement were performed in the same manner as in Example 1. One end portion of the combined bundle of the first and second optical fibers 6 and 7 is fixed to the opening 3b so as to be located * mm above the measurement region 2a, and the protruding length of the combined bundle into the reaction chamber R ′ ( 1.3 mm). Then, the humidity control gas was introduced as shown in FIG. 14C (refer to the broken line), and other than that, the RIfS measurement and the like were performed in the same manner as in Example 1. The results of Comparative Example 2 are shown in the following [Table 1] and FIG.

[Comparative Example 3]
In the comparative example 3, it performed as follows using the "constant temperature bath PDR-3KT" by ESPEC, and a dedicated humidity control apparatus. That is, without using the sealed space forming member as described above, the sensor chip 1 is directly placed in the sealed space of the thermostat and the sealed space in the thermostat and the humidity control gas delivery means 4 are connected. The first optical fibers 6 and 7 were fixed, humidity was adjusted as shown in FIG. 14E (refer to the broken line), and RifS measurement and the like were performed in the same manner as in Example 1 except that. The results of Comparative Example 3 are shown in [Table 1] below and FIG.

(Results and discussion)
As can be seen from the results in Table 1, when a generally used thermostatic chamber (Comparative Example 3 of No. 11) is used, a sufficient amount of moisture can be obtained because the humidity control gas is filled in a large space. Supplied. Therefore, although the moisture absorption amount in the two states of the dry gas and the wet gas approaches the theoretical value, on the other hand, it is difficult to continuously adjust the humidity, and fluctuations in humidity are observed locally.

  On the other hand, continuous humidity control is possible with the combination of a fine gas flow path (No. 9 comparative example 1 and No. 10 comparative example 2) and Gen-RH in which the humidity control gas flows horizontally. However, the absolute value of moisture absorption (moisture content) does not reach that of a thermostatic chamber.

  In No. 1-8 (Examples 1-8) in which the vertical gas flow path of the present invention was formed, the moisture absorption efficiency was more than that of the thermostatic chamber in a shorter time as the angle between the gas inlet and the measurement surface was closer to vertical. It can be seen that water adsorption occurs efficiently. In the case of angle (θ) = 90 °, although not shown in Table 1, it is clear that water adsorption occurs at an efficiency equal to or higher than angle (θ) = 71 °. As described above, the fact that water adsorption occurs efficiently indicates that the direction of the humidity control gas is greatly related to the reactivity when water is adsorbed on the film of the sample 2. If it is vertical, water molecules can be driven into the membrane of the sample 2, but if it is horizontal, desorption of water molecules on the surface of the sample 2 by the gas flow is promoted in the dynamic equilibrium of water adsorption / desorption. Conceivable.

《Gas capacity》
In the following Examples 9 to 11, the effect on water adsorption / desorption by changing the gas capacity of the reaction chamber (sealed space R) was examined.

[Example 9]
Example 1 except that the sensor chip 1 coated with “polymethyl methacrylate (SIGMA-ALDRICH product number“ 182230 ”)” as a sample 2 was used instead of “Fressera R” used in Examples 1 to 8. In the same manner as above, RIfS measurement and the like were performed. The results of Example 9 are shown in [Table 2] and FIG. 14 (F).

[Example 10]
RifS measurement and the like were performed in the same manner as in Example 11 except that the height of the reaction chamber (sealed space R) of the vertical gas flow path A-1 was changed to 1.5 mm. The results of Example 10 are shown in [Table 2] and FIG. 14 (F).

[Example 11]
RifS measurement and the like were performed in the same manner as in Example 11 except that the height of the reaction chamber (sealed space R) of the vertical gas flow path A-1 was changed to 5 mm. The results of Example 10 are shown in [Table 2] and FIG. 14 (F).

(Results and discussion)
From the results of Examples 9 to 11, it is understood that the condition that the gas flowing into the reaction chamber (sealed space R) is refreshed every second is preferable. When the vertical gas flow path of the semi-invention is used, it is understood that an optimum water adsorption / desorption reaction can be provided by considering the relationship with the gas flow rate.

[Example 12]
Similar to Example 11 except that the vertical gas flow path A-1 (sealed space R = 1.75 mL) of Example 9 was used and the gas flow rate was changed to 100 mL / min, 500 mL / min, and 1000 mL / min. In addition, RIfS measurement and the like were performed. The results of Example 10 are shown in [Table 3].

[Example 13]
The same as Example 11 except that the gas flow rate was changed to 100 mL / min, 500 mL / min, 1000 mL / min using the vertical gas flow path A-5 (sealed space R = 0.75 mL) of Example 10. In addition, RIfS measurement and the like were performed. The results of Example 13 are shown in [Table 3].

[Example 14]
Similar to Example 11 except that the gas flow rate was changed to 100 mL / min, 500 mL / min, 1000 mL / min using the vertical gas flow path A-6 (sealed space R = 2.5 mL) of Example 11. In addition, RIfS measurement and the like were performed. The results of Example 14 are shown in [Table 3].

[Example 15]
The height of the reaction chamber (sealed space R) of the vertical gas flow path A-1 of the example was changed to 7.5 mm, and the volume of the reaction chamber (chamber portion) (volume of the sealed space R) was formed to 3.12 mL. Then, RIFS measurement and the like were performed in the same manner as in Example 11 except that the gas flow rate was changed to 100 mL / min, 500 mL / min, and 1000 mL / min. The results of Example 15 are shown in [Table 3].

(Results and discussion)
When the gas flow rate is increased, the effect of improving the amount of water adsorption / desorption can be obtained up to a chamber volume of 2.5 ml. If the volume exceeds that, even if the gas flow rate is increased, the water adsorption / desorption efficiency of the sample 2 is not improved.

  As described above, the sealed space forming member according to the present invention, the water molecule adsorption / desorption measurement system using the same, and the water molecule adsorption / desorption measurement method have been described based on the embodiments and examples. However, the present invention is not limited to the above, and design changes are permitted without departing from the gist of the present invention defined in the claims.

DESCRIPTION OF SYMBOLS 1 Sensor chip 2 Sample 2a Measurement area 3 Sealed space formation member 3A-3G Sealed space formation member 3c Wall part 4 Humidity control gas sending means 5 Temperature / humidity sensor 5A Temperature controller 6 1st optical fiber 7 2nd optical fiber 8 Light source 9 Spectroscope DESCRIPTION OF SYMBOLS 10 Control means 11 Groove | channel 12A, 12B Gas introduction path 13 Gas guide member 13a Gas introduction port (introduction port)
13b Ring members 14A and 14B Gas discharge passage 15 Substrate 16 Optical thin film 17 Cover member 19 Temperature sensor 20 Temperature adjusting means 21 O-ring 22 Sealed space forming member 22a Gas introduction passage 22b Gas discharge passage 23 Reaction section 23a Groove 23b Gas introduction port 23c Gas outlet 24 O-ring 25 Sealed space forming member 25a Chamber part 25a Chamber part 25b Gas inlet 25ba Gas inlet 25c Gas outlet 26 O-ring 100, 100A to 100G Measurement systems R, R ', R "Sealed Space θ angle w water molecule

Claims (13)

A sealed space forming member that is used in a water molecule adsorption / desorption measurement system that measures adsorption / desorption of a sample and water molecules contained in a humidity control gas to be brought into contact with the sample, and forms a sealed space containing the sample. There,
An inlet for introducing the humidity control gas into the sealed space so as to blow the measurement region from a position facing the measurement surface portion (measurement region) of the sample;
A discharge port for discharging the humidity control gas in the sealed space to the outside of the sealed space;
A sealed space forming member comprising:   The volume of the sealed space is approximately equal to or less than the amount of the humidity control gas supplied to the sealed space during a time interval for measuring adsorption / desorption of water molecules to the sample. The sealed space forming member according to claim 1, wherein the sealed space forming member is formed.   The sealed space forming member according to claim 2, wherein a capacity of the sealed space is 1.5 mL to 3.2 mL.   4. The sealed space forming member according to claim 1, wherein the ratio of the total opening area of the introduction port to the area of the measurement region is 50: 1 to 480: 1.   The said introduction port is provided so that the said humidity control gas may be sprayed with the angle of the range of 45 degrees or more and 135 degrees or less with respect to the plane of the said measurement area | region, The any of Claims 1-4 characterized by the above-mentioned. The sealed space forming member according to claim 1. A plurality of the introduction ports are provided,
The sealed space forming member according to any one of claims 1 to 5, wherein the opening of the introduction port is at least one of a circle, an ellipse, and a rectangle.   The sealed space forming member according to claim 1, further comprising a gas guide member that guides an angle supplied to the measurement region of the flow of the humidity control gas introduced from the introduction port.   The sealed space forming member according to any one of claims 1 to 7, wherein a surface of the sealed space other than the measurement region is covered with a cover member that is more hydrophobic than the sample.   A water molecule adsorption / desorption measurement system comprising the sealed space forming member according to any one of claims 1 to 8. A sealed space having an inlet and an outlet is formed so as to enclose a sample arranged in a measurement region for measuring adsorption and desorption of the sample and water molecules, and a humidity control gas containing water molecules is introduced from the inlet. A water molecule adsorption / desorption measurement method for measuring adsorption / desorption between a thin film of the sample and the water molecules introduced into the sealed space,
A gas introduction step of introducing the humidity control gas into the sealed space through the introduction port so as to spray the humidity control gas from a position facing the measurement surface portion (measurement region) of the sample to the measurement region; A water molecule adsorption / desorption measurement method.   11. The water molecule adsorption / desorption measurement method according to claim 10, wherein the humidity control gas is blown at an angle in a range of 45 ° to 135 ° with respect to a plane of the measurement region.   The water molecule adsorption / desorption measurement method according to claim 11, wherein the humidity control gas is blown at an angle in a range of 70 ° to 110 ° with respect to a plane of the measurement region.   The water molecule adsorption / desorption measurement method according to any one of claims 10 to 12, wherein the adsorption / desorption of the sample and the water molecule is measured by RifS (reflection interference spectroscopy).