WO2000013806A1 - Method and apparatus for forming film by alternate deposition, and film-coated structure - Google Patents

Abstract

A deposition apparatus comprises a first tank (100) that holds a solution including positively charged particles, a second tank (200) that holds a solution including negatively charged particles, and a robot arm (30) that supports a film-forming material (10). The robot arm (30) includes a quartz oscillator (20) having a unique oscillation frequency. A robot arm drive (40) moves the robot arm (30) by means of a mechanical drive means along the path shown with the broken line. A deposition controller (60) operates so that the robot arm (30) may enter the first tank (100) and the second tank (200) alternately. A frequency detector (50) detects the oscillation frequency of the quartz oscillator (20). The deposition controller (60) recognizes the thickness of thin film deposited in each tank based on the change in detected frequency (f) and decides the timing of the alternation of the first and second tanks. In this manner, accurate control of deposition can be achieved.

Description

 Description Method and apparatus for manufacturing alternate adsorption film

 And structures with alternating adsorption films

 The present invention relates to an alternately adsorbed film and a method and an apparatus for producing the same, and more particularly to a light-emitting element for a display of various electronic devices, various sensors, a bio-related material such as a contact lens, a surface coating, and the like. The present invention relates to a film thickness control technique for forming an alternately adsorbed film suitable for forming a film.

¾ ^b scene art

A method using layer-by-layer electro-static self-assembly as a method for producing a composite organic thin film was announced by G. Derichi et al. In 1992 ( Decher. G, Hong JD and J. Schmit: Thin Solid Films, 210/211, p.831 (1992)). In this method, an aqueous solution of a positive electrolyte polymer (cation) and an aqueous solution of a negative electrolyte polymer (anion) are prepared in separate containers, and a substrate (film deposition) having an initial surface charge is provided in these containers. By alternately immersing the materials, a composite organic ultrathin film (alternate adsorption film) having a multilayer structure can be obtained on the substrate. For example, when a glass substrate is used as a material for forming a film, the surface of the glass substrate is subjected to a hydrophilic treatment to introduce 0H_ groups to the surface, and a negative charge is given as an initial surface charge. Then, if the substrate whose surface is negatively charged is immersed in an aqueous solution of a positive electrolyte polymer, the Coulomb force causes the positive electrolyte polymer to be adsorbed on the surface until at least the surface charge is neutralized. It is formed. The surface portion of the ultra-thin film thus formed is positively charged. Then, when this substrate is immersed in a negative electrolyte polymer aqueous solution, the negative electrolyte polymer is It will be adsorbed and one layer of ultra-thin film will be formed. In this way, by alternately immersing the substrate in the two containers, an ultra-thin layer made of a positive electrolyte polymer and an ultra-thin layer made of a negative electrolyte polymer can be formed alternately, and the multilayer structure A composite organic thin film having the following characteristics can be formed.

 Recently, M.F. J. Appl. Ph ys. 79 (10) 15 May 1996), a configuration of an automatic manufacturing apparatus for alternately adsorbed membranes has been proposed. With this device, the substrate to be a film-forming material is alternately immersed in the two water tanks by the robot arm, so that the alternate adsorption film is automatically formed on the substrate.

 The thus formed alternately adsorbed film is expected to be used for various electronic devices such as organic EL (Electro-Luminescence) devices, and by forming the alternately adsorbed film on the surface. Because it is possible to control the hydrophilicity, application to coating technology on contact lens surfaces and application to biomaterials are also attracting attention.

 At this stage, the technology for forming an alternate adsorption film described above has not yet reached practical use, and there are still issues to be solved in order to use the alternate adsorption film in commercial precision equipment such as electronic devices. ing. In particular, in order to manufacture precise electronic devices, technology for forming films while controlling the film thickness accurately is indispensable.

 Until now, film thickness control in forming an alternate adsorption film has been performed using the immersion time when immersing each electrolyte polymer in an aqueous solution. For example, a positive electrolyte polymer

—Immerse in the aqueous solution for 10 minutes, then in the negative electrolyte polymer aqueous solution for 10 minutes, again in the positive electrolyte polymer aqueous solution for 10 minutes, and so on. By alternately soaking, the thickness of each layer constituting the multilayer structure was controlled.

However, when the alternate adsorption film is repeatedly formed many times, It has been found that the distance and the film thickness do not always have a linear relationship. For example, one immersion time is defined as 10 minutes, and alternate immersion is repeated alternately in the positive and negative electrolyte polymer aqueous solutions.A total of 10 immersions results in an alternately adsorbed film with a total thickness of 10 O nm. Let's say In this case, even if the alternate immersion is performed a total of 20 times under exactly the same conditions, the total thickness of the obtained alternately adsorbed film does not reach 20 O nm, and in practice, for example, the thickness of 300 nm is reduced. The resulting alternately adsorbed film is formed. As described above, since the deposition rate changes depending on the number of times of adsorption, when a plurality of layers are alternately formed, the relationship between the immersion time and the film thickness becomes a non-linear relationship. According to the experiment performed by the inventor of the present invention, it was found that the film formation rate was generally low when the number of times of adsorption was small, and the film formation rate tended to increase as the number of times of adsorption was increased. Moreover, it was confirmed that the specific characteristics of such a nonlinear relationship differed depending on the type of material used. As a result, the conventional method of controlling the film thickness by the immersion time cannot accurately control the film thickness, which is a serious problem when mass-producing precise electronic devices. Accordingly, an object of the present invention is to provide a method and an apparatus for manufacturing an alternately adsorbed film capable of accurately controlling the film thickness, and a useful alternately adsorbed film that can be realized by such accurate film thickness control. It is an object to provide a structure having: Disclosure of the invention

 (1) The first aspect of the present invention provides an alternately adsorbed film having a multilayer structure by alternately immersing a film-forming material a plurality of times in a solution containing positively charged particles and a solution containing negatively charged particles. In the method for producing an alternate adsorption film for producing

 When the material to be film-formed is put in and taken out of each solution, the crystal unit is taken in and out at the same time. When the value f ref is reached, or when the change rate V of the oscillation frequency reaches a predetermined reference value Vref, the solution is taken out of the solution.

(2) A second embodiment of the present invention includes a solution containing positively charged particles and a negatively charged particle. A method for producing an alternately adsorbed film having a multilayer structure by alternately immersing a film-forming material in a solution and a plurality of times,

 When the material to be film-formed is taken in and out of each solution, the crystal unit is taken in and out at the same time. The liquid is taken out of the solution when Z ref is reached or when the rate of change of impedance VZ reaches a predetermined reference value V z ref.

 (3) The third aspect of the present invention is directed to an alternately adsorbed film having a multilayer structure by alternately immersing a film-forming material a plurality of times in a solution containing positively charged particles and a solution containing negatively charged particles. In an alternate adsorption film manufacturing apparatus for manufacturing

 A first tank for containing a solution containing positively charged particles;

 A second tank for containing a solution containing negatively charged particles;

 A robot arm for holding a film-forming material,

 A robot arm driving section for driving a robot arm so that the material to be film-formed is alternately in a state of being immersed in the solution in the first tank and a state of being immersed in the solution in the second tank. ,

 A quartz oscillator attached to the robot arm so that it is immersed in each solution together with the material to be deposited,

 A frequency detector for detecting the oscillation frequency of the crystal unit,

 A film formation control unit for controlling a robot arm drive unit based on the frequency detected by the frequency detection unit;

 Is provided.

 (4) A fourth aspect of the present invention is the apparatus for manufacturing an alternate adsorption film according to the third aspect described above,

An ultrasonic generator for applying ultrasonic vibration to the solution contained in the tank is further provided. (5) A fifth aspect of the present invention is the manufacturing apparatus for an alternate adsorption film according to the third aspect described above,

 A counter electrode that can be immersed in the solution in the tank,

 A voltage applying unit for applying a voltage between the film-forming material and the quartz oscillator and the counter electrode;

 Is further provided.

 (6) In a sixth aspect of the present invention, a film-forming material is alternately immersed a plurality of times in a solution containing first charged particles and a solution containing second charged particles having different electric polarities. In a structure having an alternately adsorbed film formed by

 The structure is such that the thickness of each layer of the alternating adsorption film monotonically increases or monotonically decreases from the deep portion to the surface.

 (7) In a seventh aspect of the present invention, a film-forming material is alternately immersed a plurality of times in a solution containing first charged particles and a solution containing second charged particles having different electric polarities. In a structure having an alternately adsorbed film formed by

 The thickness of the layer containing the first charged particles is set so that the physical properties of the second charged particles are dominant in the entire layer of the alternating adsorption film. It is configured so as to be sufficiently smaller than.

 (8) According to an eighth aspect of the present invention, a film-forming material is alternately immersed a plurality of times in a solution containing first charged particles and a solution containing second charged particles having mutually different electrical polarities. In a structure having an alternately adsorbed film formed by

 The thickness of each layer containing the first charged particles monotonously decreases from the deep part to the surface, and the thickness of each layer containing the second charged particles monotonically increases from the deep part to the surface. .

(9) According to a ninth aspect of the present invention, a film-forming material is alternately immersed a plurality of times in a liquid containing positively charged particles and a liquid containing negatively charged particles to form an alternately adsorbing film having a multilayer structure. In the method for producing an alternate adsorption film to be produced, By wrapping uncharged particles or particles that have only an insufficient charge to perform alternate adsorption with a plurality of charged molecules, a sufficient charge to perform alternate adsorption as a whole is obtained. A liquid in which charged particles are formed and the charged particles are dispersed in a liquid is used as one or both of a first liquid and a second liquid.

 (10) A tenth aspect of the present invention is directed to the method for producing an alternate adsorption film according to the ninth aspect,

 By dispersing ferrite fine particles or metal complex fine particles and a surfactant in water, micelles wrapped around the fine particles with surfactant molecules are formed, and the micelles are used as charged particles. is there. Brief explanation of drawings

 FIG. 1 is a conceptual diagram showing the principle of manufacturing a general alternating adsorption film.

 2 (a), 2 (b) and 2 (c) are conceptual diagrams showing a state in which an electrolyte polymer is adsorbed on the surface of the substrate 10 based on the manufacturing principle shown in FIG.

 FIG. 3 is a conceptual diagram showing a more specific adsorption state in the second immersion treatment based on the manufacturing principle shown in FIG.

 FIG. 4 is a conceptual diagram showing a structure of an alternate adsorption film formed when the immersion treatment shown in FIG. 3 is performed six times in total.

 FIG. 5 is a graph showing a non-linear relationship between the immersion time and the film thickness when a multi-layer alternately adsorbing film is formed.

 FIG. 6 is a view showing a crystal unit and a frequency detection unit used for carrying out the manufacturing method according to the present invention.

 FIG. 7 is a block diagram showing a basic configuration of an apparatus for manufacturing an alternate adsorption film according to the present invention.

Figure 8 shows an alternate suction structure with a uniform mouth structure so that the thickness of each layer is uniform. It is a conceptual diagram which shows a film deposition.

 FIG. 9 is a conceptual diagram showing an alternating adsorption film in which the thickness of each layer monotonically decreases from the deep part to the surface.

 FIG. 10 is a concept showing an alternate adsorption film set so that the film thickness of each layer A made of the first electrolyte polymer is sufficiently smaller than the film thickness of each layer B made of the second electrolyte polymer. FIG.

 Fig. 11 shows that the thickness of each layer A of the first electrolyte polymer decreases monotonically as it goes from the deep part to the surface, and the thickness of each layer B of the second electrolyte polymer monotonically increases as it goes from the deep part to the surface. It is a conceptual diagram which shows such an alternate adsorption film.

 FIGS. 12 (a) and (b) are schematic diagrams showing the configurations of ferrite fine particles and a surfactant.

 FIG. 13 is a schematic diagram showing the structure of a micelle formed by enclosing the ferrite fine particles shown in FIG. 12 (a) with the surfactant shown in FIG. 12 (b). FIG. 14 is a configuration diagram showing an example of an apparatus for manufacturing an alternate adsorption film having a function of giving an initial surface charge by a physical method. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described based on an illustrated embodiment.

 8 1. General manufacturing method of cross-adsorption membrane

FIG. 1 is a conceptual diagram showing the principle of manufacturing a general alternating adsorption film. In the figure, a first tank 100 contains an aqueous solution of a positive electrolyte polymer (cation), and a second tank 200 contains an aqueous solution of a negative electrolyte polymer (anion). Is included. Here, a substrate 10 made of, for example, glass or silicon is prepared as a film-forming material, and its surface is subjected to a hydrophilic treatment to introduce an OH group into the surface, thereby giving a negative charge as an initial surface charge. . FIG. 2 (a) is a conceptual diagram showing a state where the surface of the substrate 10 is negatively charged. Then, this negatively charged substrate When 10 is put in the first tank 100, the positive electrolyte polymer comes into contact with the surface of the substrate 10 and is adsorbed by Coulomb force. FIG. 2 (b) is a conceptual diagram showing a state where the positive electrolyte polymer is adsorbed. Here, when the substrate 10 is put into the second tank 200, the negative electrolyte polymer comes into contact with the surface of the substrate 10 and is adsorbed by Coulomb force. FIG. 2 (c) is a conceptual diagram showing a state where the negative electrolyte polymer is adsorbed. As described above, when the substrate 10 is alternately immersed in the first tank 100 and the second tank 200, a layer made of a positive electrolyte polymer is formed on the surface of the substrate 10. The layers composed of the negative electrolyte polymer are formed alternately, and finally the alternately adsorbed film having the multilayer structure is formed.

 However, the conceptual diagram shown in Fig. 2 shows a simplified model to explain the principle, and in practice, thin film formation is performed in a state close to the conceptual diagram shown in Fig. 3 or 4. It seems to be done. FIG. 3 is a conceptual diagram showing an adsorption state in a second immersion process (a process in which the substrate 10 is taken out of the first tank 100 and immersed in the second tank 200). . On the surface of the substrate 10, a first thin film A 1 made of a positive electrolyte polymer has already been formed by the first immersion treatment. The negative electrolyte polymer b in the tank 200 will be adsorbed on the surface. If the substrate 10 is immersed in the second tank 200 for a certain period of time, the negative electrolyte polymer b in the second tank 200 is successively adsorbed on the surface, and the second thin film is formed. B 2 will be formed. However, after a certain period of time, when the second thin film B2 made of the negative electrolyte polymer b becomes thicker, the Coulomb force by the thin film A1 no longer acts, and the adsorption is saturated at that point. You will reach the point.

The repulsion due to the Coulomb force between segments within one polymer molecule changes depending on the conditions such as the concentration of the electrolyte polymer used in this adsorption process, the pH value, and the adsorption time. Density will depend on these conditions. Therefore, depending on the setting of these conditions, It is possible to form always thin films or relatively thick films. FIG. 4 is a conceptual diagram showing the structure of an alternate adsorption film formed when such immersion treatment is performed a total of six times. Here, the thin films A 1, A 3, A 5 constituting the odd-numbered layers are layers composed of a positive electrolyte polymer, and the thin films B 2, B 4, B 6 constituting the even-numbered layers are negative. This is a layer made of an electrolyte polymer. The thickness of each of these layers can be controlled by the time of the immersion treatment. As described above, when the thickness reaches a certain thickness, the Coulomb force stops working due to electrical neutralization, and the adsorption reaches the saturation point, but until this saturation point is reached, the immersion time is long. The longer, the thicker the film thickness. Therefore, conventionally, the film thickness was controlled by the immersion time.

 However, as described above, when a multi-layer alternate adsorption film is formed, the immersion time and the film thickness actually show a non-linear relationship. FIG. 5 is a graph showing an example of this nonlinear relationship. In this graph, one immersion time was set to 10 minutes, and the process of alternately immersing the substrate 10 in the first tank 100 and the second tank 200 was repeatedly executed continuously. FIG. 9 shows a time change of the total film thickness of the alternate adsorption film formed in the case. In the example of this graph, the film formation rate was slow while the number of adsorptions was small, and gradually increased as the number of adsorptions increased, and a substantially linear relationship was obtained after 2000 sec. Such characteristics vary depending on the type of material used and the concentration of the aqueous solution, and the graph shown in the drawings does not necessarily indicate general characteristics. In any case, if the thickness is controlled by the immersion time, accurate control cannot be performed.

 S2. Method for producing alternate adsorption film according to the present invention

The gist of the present invention is that the thickness of the thin film formed on the substrate 10 is directly detected using a quartz oscillator. Now, a disk-shaped crystal resonator 20 as shown in FIG. 6 is prepared, and electrodes 21 made of metal (eg, gold, silver, etc.) are formed on the upper and lower surfaces thereof. The crystal oscillator 20 has its own oscillation frequency By applying a predetermined electric signal to the pair of upper and lower electrodes 21 from the frequency detection unit 50 (specifically, an electronic circuit having a frequency counter), The frequency f can be detected.

 Here, if such a crystal resonator 20 itself is used as a material for film formation and is alternately put into and taken out of the first tank 100 and the second tank 200, an alternately adsorbed film is formed on the surface of the substrate 10. In the same manner as when the crystal is formed, an alternate adsorption film is also formed on the surface of the crystal unit 20. When a thin film is formed on the surface of the crystal unit 20 in this way, a change occurs in the inherent oscillation frequency f. Moreover, a linear relationship holds between the frequency f and the thickness of the formed thin film. Strictly speaking, a linear relationship holds between the mass of the crystal unit 20 (the total mass including the formed thin film) and the oscillation frequency. By using a disk-shaped crystal unit whose thickness is sufficiently small, the thickness of the thin film formed on both the upper and lower surfaces and the total mass of the crystal unit 20 including this thin film can be substantially reduced. Since the linear relationship holds, practically, there is no problem even if the amount of change in the oscillation frequency f detected by the frequency detector 50 is treated as an amount indicating the grown film thickness.

 After all, the crystal unit 20 is treated as one film-forming material as well as the substrate 10 as the original film-forming material, and the surface initial charge is applied to the substrate 10 and the crystal unit 20. If the two aqueous solutions are alternately taken in and out, an alternate adsorption film is also formed on the quartz oscillator 20 at the same film formation rate as the film formation rate on the substrate 10. Moreover, the thickness of the alternately adsorbed film formed on the crystal unit 20 can be measured in real time during the film forming process by the frequency detecting unit 50 as the variation 発 振 f of the oscillation frequency f. . The film thickness measured in this way is much more accurate than the film thickness measured indirectly based on the immersion time, and a nonlinear relationship like the graph shown in Fig. 5 may occur. No problem occurs.

Theoretically, if the mass of the crystal unit 20 changes by 1 ng, the oscillation frequency f will change by 1 Hz. So, for example, the crystal formed on the surface of the crystal unit 20 If the thickness of the deposited thin film is increased by 1 nm, and the mass of the crystal unit 20 is set to increase by In, then the change in the oscillation frequency f = 1 Η 、 This corresponds to a change in thickness of 1 nm. If such a setting is made, for example, in the example shown in FIG. 4, if the thickness of the first layer film A1 is to be 100 nm, the following film formation control is performed. Just do it. First, the substrate 10 and the crystal unit 20 whose surfaces are negatively charged are immersed in the first tank 100, and the oscillation frequency f of the crystal unit 20 at the start of immersion (for example, f = 10 × 10 ^βとIs measured by the frequency detector 50. Then, while forming the thin film A1 in the first tank 100 as it is, the detection frequency f by the frequency detection unit 50 was monitored, and when f = 9999900 Hz (variation Δΐ = --100 Hz), the substrate was By performing a process of pulling up the crystal unit 10 and the crystal unit 20 from the first tank 100, a thin film 81 having a thickness of 100] 111 is obtained.

 Subsequently, if it is desired to control the thickness of the second thin film B 2 to be 200 nm, the substrate 10 and the crystal unit 20 pulled up from the first tank 100 should be It is immersed in the second tank 200, and the oscillation frequency f of the crystal oscillator 2 ° at the start of the immersion is measured by the frequency detection unit 50 in advance. Here, let's say that f = 9999900Hz. While the thin film B 2 is being formed in the second tank 200 as it is, the detection frequency f detected by the frequency detection unit 50 is monitored, and when f = 9999700 Hz (change amount △ f =-200 Hz) Then, if the substrate 10 and the crystal unit 20 are pulled up from the first tank 100, a thin film B2 having a thickness of 200 nm can be obtained.

Eventually, the crystal oscillator 20 is moved into and out of the aqueous solution at the same time as the substrate 10, and the variation 発 振 f of the oscillation frequency of the crystal oscillator with respect to the time when the crystal oscillator 20 is introduced reaches the predetermined reference value: fref. At this point, if control is performed so that both are removed from the aqueous solution, an arbitrary film thickness can be obtained depending on the setting of the reference value fref. Note that, as will be described in an embodiment to be described later, usually, when the substrate 10 and the crystal unit 20 are moved from the first tank 100 to the second tank 200, or when the second tank When moving from 100 to the first tank 100, a rinse bath of pure water or the like is used, so that the excessively absorbed electrolyte polymer is removed and the film thickness is slightly reduced. Therefore, when strict film thickness accuracy is required, it is necessary to set the reference value f ref in consideration of the film thickness reduced by the rinsing bath. In order to ensure strict film thickness accuracy, after rinsing, monitor the film thickness by stabilizing the substrate 10 and the crystal unit 20 in the rinsing bath. If the film thickness has also decreased, it can be controlled to return to the original polymer tank before the rinsing bath and increase the film thickness.

 § 3. An apparatus for manufacturing an alternate adsorption film according to the present invention

 As described above, the method for manufacturing an alternate adsorption film according to the present invention has been described. Next, an apparatus for manufacturing an alternate adsorption film using this method will be described. FIG. 7 is a block diagram showing a basic configuration of an apparatus for producing the alternately adsorbed film. If predetermined film forming conditions are set in advance using this manufacturing apparatus, a film forming process based on the film forming conditions will automatically proceed.

The basic components of this manufacturing apparatus are a first tank 100, a second tank 200, a crystal oscillator 20, a robot arm 30, a robot arm drive unit 40, and a frequency A number detection unit 50, a film formation control unit 60, and an ultrasonic wave generation unit 70. The first tank 100 is a tank for storing a positive aqueous solution of the electrolyte polymer, and the inside is divided into four storage tanks 110 to 140. Here, the storage tank 110 is the original tank for storing the positive electrolyte polymer aqueous solution, and the remaining storage tanks 120, 130, and 140 are for the rinse bath filled with pure water. It is a tank. On the other hand, the second tank 200 is a tank for storing a negative electrolyte polymer aqueous solution, and the inside is divided into four storage tanks 210 to 240. Here, the storage tank 210 is the original tank for storing the negative electrolyte polymer aqueous solution, and the remaining storage tanks 220, 230, 240 are filled with pure water. It is a bath for the rinse bath. The substrate 10 and the quartz oscillator 20 pulled out of the electrolyte polymer aqueous solution tank are sequentially immersed in three rinse baths containing pure water, and the attached aqueous solution is washed away, Excessively adsorbed electrolyte polymer is also removed. As a result, only the electrolyte polymer firmly adsorbed by the Coulomb force remains on the substrate 10.

 The crystal resonator 20 is the crystal resonator described with reference to FIG. 6, and has a unique oscillation frequency. The robot 30 has a function of holding and moving the substrate 10 as a film-forming material. The crystal oscillator 20 is attached to the robot arm 30 and is fixed at a position where the crystal oscillator 20 is simultaneously immersed when the substrate 10 is immersed in an aqueous solution or pure water. Have been.

 The robot arm driving unit 40 is configured so that the substrate 10 and the crystal unit 20 are immersed in the liquid in the first tank 100 and in the liquid in the second tank 200. This is a mechanism for driving the robot arm 30 so as to take turns alternately. The path shown by the broken line in the figure indicates the movement path of the robot arm 30. That is, the mouth bot arm drive unit 40 moves the robot arm 30 sequentially along the following route. First, a layer made of a positive electrolyte polymer is formed by immersion in the storage tank 110 in the first tank 100, and subsequently, the storage tanks 120, 130, and 140 are formed. Soak in rinse bath in order of 0. Subsequently, a layer made of a negative electrolyte polymer is formed by immersion in the storage tank 210 in the second tank 200, and subsequently, the storage tanks 220, 230, and 24 are formed. Soak in rinse bath in order of 0. After making one round, return to the storage tank 110 in the first tank 100 again.

The frequency detector 50 is an electronic circuit having a frequency counter as described with reference to FIG. 6, and has a function of detecting the oscillation frequency f inherent to the crystal unit 20. The oscillation frequency detected here is given to the film forming control unit 60. The film formation control unit 60 is actually configured by a computer on which a predetermined film formation control program is installed, and the frequency change detected by the frequency detection unit 50 is changed. It has a function of outputting a control signal for controlling the robot arm driving section 40 based on the amount of conversion. The robot arm 30 makes a single round of movement (moving in the horizontal direction in the figure and moving vertically in and out of each tank) along the path shown by the broken line in FIG. It will be controlled by the control unit 6◦.

 The ultrasonic generator 70 is a component for applying ultrasonic waves to the tanks 110 and 210, and can apply ultrasonic vibration to the solution in each tank. Such ultrasonic waves are useful when using a solution containing components that are difficult to disperse uniformly. In particular, it is extremely useful when forming an alternately adsorbed film using a mist solution described later, and details thereof will be described in §5.

 In FIG. 7, the broken line indicates the movement path of the robot arm 30 as described above, the dashed-dotted arrow indicates transmission of mechanical driving force and vibration, and the solid-line arrow indicates transmission of electric signals. Is shown.

 By using such an apparatus, it is possible to manufacture an alternately adsorbed film composed of a thin film having an arbitrary thickness in accordance with the setting of a program provided in a computer constituting the film forming control unit 60. . Of course, as a program prepared in the film formation controller 60, an operation for controlling the timing of taking in and out of each tank can be performed according to the immersion time. For example, containment tank 110 for 10 minutes, containment tank 120 for 2 minutes, containment tank 130 for 1 minute, containment tank 140 for 1 minute, containment tank 210 for 10 minutes, If you prepare a program with settings such as 2 minutes in the tank 220, 1 minute in the storage tank 230, and 1 minute in the storage tank 240, the positive and negative electrolyte polymers will be deviated from each other. After adsorption for 0 minutes, a rinsing bath for 2 minutes, 1 minute, and 1 minute is performed.

Of course, in carrying out the original manufacturing method of the present invention, the timing control of taking in and out of each tank is performed based on the variation Δί of the oscillation frequency f given from the frequency detecting section 50. In other words, the timing of taking in and out of the rinsing bath can be controlled by the time as described above, but there is no problem. With respect to this, control is performed so that the frequency change amount △ f from the time when the battery is put into the tank reaches a predetermined reference value f ref (corresponding to a predetermined film thickness), and is raised. . As described above, if the control based on the variation Δ 量 of the oscillation frequency f is performed, it is possible to accurately form an alternate adsorption film having an arbitrary thickness.

 If a blower (for example, a device that blows nitrogen gas) for drying the surface of the substrate 10 lifted from the rinsing bath is provided, the water droplets adhering to the surface of the substrate 10 are sufficiently removed. Then, the process can be shifted to the next layer. Alternatively, a dedicated tank for drying (for example, a drying room equipped with a mechanism for blowing hot air) is provided, and the substrate 10 pulled up from the rinsing bath is put into this dedicated tank to ensure sufficient drying. May be performed.

 As described above, according to the method and the apparatus for manufacturing the alternately adsorbed film according to the present invention, the film thickness is directly measured by the quartz oscillator, so that accurate film thickness control becomes possible. Further, it is possible to obtain a structure having a useful alternating adsorption film that can be realized by such accurate film thickness control.

 S 4. Structure with alternating adsorption film

 As described above, the use of the method and the apparatus for manufacturing an alternate adsorption film according to the present invention enables high-precision control of the thickness, thereby forming an alternate adsorption film suitable for a special use. This makes it possible to manufacture an alternately adsorbed membrane structure suitable for special applications. Hereinafter, some examples of the structure having such a special alternating adsorption film will be described.

First, FIG. 8 is a conceptual diagram showing an example in which an alternately adsorbing film having a uniform opening structure is formed on a substrate 10 so that the thickness of each layer is uniform. Here, the thin film A is a layer formed by a first electrolyte polymer aqueous solution (for example, a positive electrolyte polymer aqueous solution), and the thin film B is a second electrolyte polymer aqueous solution (for example, a negative electrolyte polymer). (Aqueous solution). The thickness of the thin film A and the thickness of the thin film B are uniform in all layers. This is the oscillation frequency This is the result of forming a film with the reference value: ref always set to a constant value for the change amount Δί of the wave number. As described above, the structure having the alternately adsorbed film in which the thickness of each layer is uniform can be used as various light-emitting elements, and in particular, can be used for a high-quality ultra-thin plastic display and the like. become.

 On the other hand, FIG. 9 is a conceptual diagram showing an example in which an alternately adsorbed film is formed on the substrate 10 such that the thickness of each layer monotonically decreases from the deep portion to the surface. The thin film A is formed by a first electrolyte polymer aqueous solution, and the thin film B is a layer formed by a second electrolyte polymer aqueous solution, as in the example of FIG. 8. It is thinner as it goes to the surface. Conversely, it is also possible to form an alternately adsorbed film that monotonically increases from the deep portion to the surface. In order to manufacture such an alternating adsorption film, a function that monotonically increases or monotonically decreases as the number of times of immersion treatment increases as the reference value f ref. The alternating adsorption film having such properties can be used for an optical waveguide, a refractive index distribution type optical fiber, and the like.

FIG. 10 shows the thickness of each layer A made of the first electrolyte polymer on the substrate 10 so that the physical properties of the second electrolyte polymer are dominant in the entire alternating adsorption film. FIG. 3 is a conceptual diagram showing an example in which an alternate adsorption film is set so as to be sufficiently smaller than the thickness of each layer B made of a second electrolyte polymer. As shown, the thickness of the layer A is much smaller than the thickness of the layer B, so that the layer A merely functions as an adhesive between the layers B. In such an alternately adsorbed film, the physical properties of the second electrolyte polymer constituting the layer B become dominant, so only the physical properties of one material are shown despite the fact that it is a composite organic thin film. It can function as a thin film. In order to manufacture such an alternately adsorbed film, different values may be set as the reference value f ref for the odd-numbered immersion treatment and the even-numbered immersion treatment. The alternating adsorption film having such properties can be used for an organic EL (light emitting) device, a biosensor, and the like. FIG. 11 shows that the thickness of each layer A of the first electrolyte polymer monotonously decreases from the depth to the surface of the substrate 10, and the thickness of each layer B of the second electrolyte polymer decreases from the depth. FIG. 5 is a conceptual diagram showing an example in which an alternate adsorption film is formed such that it increases monotonically as it goes to the surface. In order to manufacture such an alternately adsorbed film, a function that monotonically decreases as the number of times of immersion treatment is set in the odd number of immersion treatments as the reference value f ref, What is necessary is just to set a function that increases monotonically with each repetition. In such an alternating adsorption film, the physical properties of the first electrolyte polymer become more prominent as it goes deeper, and the physical properties of the second electrolyte polymer become more prominent as it goes closer to the surface. It is possible to provide new functions that were not found in the alternate adsorption film. For example, if polymer materials having different refractive indices are used as the first electrolyte polymer and the second electrolyte polymer, a thin film whose refractive index gradually changes from the deep portion to the surface can be obtained. Such a thin film can be applied to a refractive index distribution type optical fiber or the like. Alternatively, if an insulating material is used as the first electrolyte polymer and a conductive material is used as the second electrolyte polymer, a thin film whose conductivity gradually changes from the deep portion to the surface can be obtained. become. In other words, a thin film having high insulating properties at the deep portion and exhibiting conductivity only at the surface portion can be obtained. Conversely, it is also possible to obtain a thin film in which the deep part has high conductivity and only the surface part has insulating properties. Such a thin film can be applied to a printed circuit board, an integrated circuit, and the like.

 § 5. Other embodiments and embodiments

In the above-described embodiment, the positive electrolyte polymer aqueous solution and the negative electrolyte polymer aqueous solution are prepared one by one, and are alternately immersed in them to form an alternating adsorption film. It is also possible to prepare a plurality of them and select and use these as appropriate. For example, in the example shown in FIG. 7, the storage tank 110 is further divided into a plurality of tanks, and each tank has a different type of positive electrode. Similarly, the storage tank 210 is further divided into a plurality of tanks, and different kinds of negative electrolyte polymer aqueous solutions are prepared in the respective tanks. When the substrate 10 and the crystal unit 20 are immersed in the storage tank 110 or 210, the substrate 10 and the crystal unit 20 are selectively immersed in any one of the plurality of aqueous solution tanks. By adopting such a method, it becomes possible to select the most suitable aqueous solution for the layer to be formed every time.

By preparing a plurality of types of aqueous solutions by changing the type of polymer contained, the force ^s that can form an alternate adsorption film having a different molecular component for each layer ^s . Thus, the method is not limited to the method of changing the kind of the polymer itself. That is, even when an aqueous solution containing the same polymer is used, plural kinds of aqueous solutions can be prepared by changing various conditions. For example, even when an aqueous solution containing the same polymer is used, changing the pH value will change the properties of the film formed by adsorption. Since the pH value of an aqueous solution is a parameter that affects the repulsive force between molecules, it is possible to change the density of the adsorption film by changing the pH value. Therefore, an aqueous solution having a pH value suitable for forming a thick film and an aqueous solution having a pH value suitable for forming a thin film are prepared, and according to the thickness of the layer to be formed. By selectively immersing the film in any one of the aqueous solutions, the film can be formed under more preferable conditions. In the process of forming an alternately adsorbed film, if the Coulomb force stops acting due to electrical neutralization, the film will no longer grow thereafter, and the thickness will be saturated. Therefore, when a particularly thick layer is to be formed, it is essential to immerse the film in an aqueous solution having a pH value suitable for forming a thick film.

The conditions of the aqueous solution vary depending not only on the above-mentioned pH value but also on the concentration and temperature. Therefore, it is possible to prepare a film under favorable conditions by preparing a plurality of aqueous solutions having different concentrations or temperatures and selectively immersing them in an aqueous solution suitable for each layer when alternately immersing in a tank. become. It should be noted that the physical quantity detected by the crystal unit 20 is merely the mass of the film, not the thickness of the film. Therefore, if the density of the formed adsorbent layer changes by changing the conditions such as the pH value, concentration, and temperature of the aqueous solution, the relationship between the mass and the thickness also changes. Therefore, when using multiple aqueous solutions with different conditions such as pH value, concentration, temperature, etc., grasp the relationship between mass and thickness for each aqueous solution in advance, and determine the timing for taking in and out of the aqueous solution. It is preferable to take this into consideration.

 In addition, it was confirmed that the thickness of each adsorption layer also changed depending on the drying process after the rinsing bath. When using the device shown in Fig. 7, remove from the rinsing bath storage tank 140 and then transfer it to the negative electrolyte polymer tank 210 or from the rinsing bath storage bath 240. After removal, it is preferable to add a drying step for a predetermined time when transferring to the positive electrolyte polymer tank 110.However, as long as the inventor of the present application has confirmed, if this drying step is made longer, However, a slight increase in the film thickness was observed. Therefore, as described above, the film formation conditions are controlled not only by changing the conditions such as the pH value, concentration, and temperature of the aqueous solution, but also by changing the drying time after the rinsing bath. It is also possible to do.

In the embodiments described above, the timing of taking out the substrate 10 and the crystal unit 20 from the polymer aqueous solution is based on the change amount of the oscillation frequency of the crystal unit 20 with respect to the time when the substrate 10 and the crystal unit 20 are put into the polymer aqueous solution. Is reached at a predetermined reference value f ref, but instead may be set at a time at which the oscillation frequency change speed V reaches a predetermined reference value V ref. Initially, when the substrate 10 and the crystal unit 20 were immersed in the aqueous polymer solution, the polymer in the aqueous solution was actively adsorbed on the surfaces of the substrate 10 and the crystal unit 20 by the action of Coulomb force. The film speed is relatively high. For this reason, the change speed V of the oscillation frequency of the crystal unit 20 is relatively high. However, as the film formation process progresses, Coulomba gradually decreases due to electrical neutralization, and the film formation speed gradually decreases. Will be. For this reason, the change rate v of the oscillation frequency of the crystal unit 20 gradually decreases, and when the film forming process reaches a saturation state, the change rate V of the oscillation frequency theoretically becomes zero. become. Therefore, by monitoring the change speed V of the oscillation frequency, it is possible to recognize whether or not the film formation process has reached a saturation state. That is, the change amount of the oscillation frequency per unit time is defined as a change speed V, and when the change speed V decreases to a predetermined reference value vref, it is determined that the film forming process has reached a saturated state, and What is necessary is just to take out 10 and crystal oscillator 20 from polymer aqueous solution.

 When the polymer is taken out from the aqueous polymer solution at such a timing, it is possible to form an alternately adsorbed film in which the thickness of each layer is maximized. For example, in the case of the example shown in FIG. 4, a thin film layer A1 is formed by immersing a substrate 10 having a negatively charged surface in a positive electrolyte polymer aqueous solution. At this time, the oscillation frequency of the crystal oscillator 20 immersed together with the substrate 10 is monitored, and the rate of change V of the oscillation frequency is adjusted to a predetermined reference value vref (an appropriate value that can determine that the film forming process has almost reached a saturated state). Value) (for example, if the frequency change for one minute is within 1 Hz), the substrate 10 and the crystal unit 20 may be lifted from the polymer aqueous solution. The thin film layer A1 formed at this time has a substantially maximum thickness because the film forming process is substantially saturated. Subsequently, the substrate 10 and the crystal unit 20 are immersed in a negative electrolyte polymer aqueous solution.In this case as well, when the change rate V of the oscillation frequency falls to the predetermined reference value vref, the substrate 10 and the crystal unit 20 are raised. do it.

As described above, if the adsorption is performed until the film formation process becomes substantially saturated, a uniform thin film layer having no variation in charge distribution can be formed. This is because the charge of the next lower layer does not affect the film formation step of forming the next thin film layer on the surface of a certain thin film layer. For example, in FIG. 4, in the film forming step of forming the second thin film layer B 2, adsorption is performed until the film forming process is saturated. In this case, the influence of the charge of the first thin film layer A 1 which is one layer below is completely canceled out by the second thin film layer B 2, so that the third thin film layer A 3 is formed. At the stage of growth, the charge of the first thin layer A 1 is completely unaffected. As described above, conventionally, the timing of withdrawal from the polymer aqueous solution was controlled by the immersion time. Therefore, it was necessary to secure a sufficiently long immersion time in order to bring the film formation process to a saturated state. For example, if the immersion time in each polymer aqueous solution is set to 1 hour, almost saturated conditions will be reached under any film formation conditions, and as described above, the alternately adsorbed layers having the maximum film thickness for each layer will be used. Can be formed. However, depending on the film formation conditions, saturation may be reached in as little as 5 minutes, and in such a case, the conventional method wastes more than 10 times the actually required immersion time. Will be. On the other hand, in the above-described method according to the present invention, the fact that the saturated state has been reached can be recognized based on the change speed V of the oscillation frequency of the crystal resonator 20, so that the unnecessary film formation time is reduced. Efficient production can be performed with savings.

Further, according to an experiment performed by the present inventors, it was confirmed that as the film formation process progressed on the surface of the crystal unit 20, the impedance of the crystal unit 20 changed. . That is, as the film thickness of the adsorption film formed on the surface of the crystal unit 20 increases, the impedance also increases. For example, use an impedance detector instead of the frequency detector 50 shown in Fig. 6 to observe the current value while applying an AC voltage between the electrodes formed on both sides of the crystal unit 20. Thus, the impedance Z between both electrodes can be detected. Then, when the amount of change Δ イ ン ピ ー ダ ン ス in impedance of the crystal unit 20 reaches a predetermined reference value Z ref with respect to the time when it is put into the solution, or when the rate of change of impedance V z is If the solution is taken out from the solution when the value reaches the value V z ref, the thickness of each adsorption layer can be controlled to a desired thickness. Of course, practically, control based on the frequency of the crystal unit 20 and control based on the impedance By combining this with control, more accurate film thickness control becomes possible.

In the examples described above, the alternately adsorbed film is formed by alternately immersing the film-forming material in the aqueous solution of the positive electrolyte polymer and the aqueous solution of the negative electrolyte polymer. Then, it is not always necessary to use an aqueous solution of the electrolyte polymer. For example, aqueous solution of ruthenium complex monomer _{(R u (bpy) 3 C} 1 2) and (positively charged monomers one aqueous), polyacrylic acid - (the charged polymer solution negatively) an aqueous solution of (poly acrylic acid) By alternately immersing the film-forming materials, it is possible to form an alternately-adsorbed film. Even if an electrolyte monomer is used in place of the electrolyte polymer, the alternately-adsorbed film can be formed. The ruthenium complex described above is also soluble in organic solvents such as ethanol, acetone, dimethylformamide, pyridine, and acetonitrile. Therefore, a solution using an organic solvent may be used instead of the aqueous solution.

 The inventor of the present application has further found that an alternate adsorption film can be formed even by using a solution in which ferrite fine particles, metal complex fine particles, and the like are dispersed in a charged state. For example, ferrite fine particles as shown in Fig.

2 When a surfactant (amphiphilic substance) with a positive charge as shown in Fig. (B) and water are dispersed in water, the surfactant around the ferrite fine particles is dispersed as shown in Fig. 13 The agents associate around (positively charged hydrophilic groups point outward), yielding an aqueous solution of micelles whose surface is positively charged. In this case, as shown in the figure, micelles around a single ferrite fine particle surrounded by a surfactant may be formed, or micelles surrounded by a plurality of ferrite fine particles around a surfactant may be formed. May be formed. Such a micelle aqueous solution performs the same function as the positive electrolyte polymer aqueous solution in the examples described above, and can be used for forming an alternate adsorption film. Of course, if a surfactant having a negative charge on the hydrophilic group (for example, arachidic acid) is used, a micellar aqueous solution having a negative charge can be obtained. The negative charge in the example It will perform the same function as the degraded polymer aqueous solution. As a result, the present invention provides a solution containing positively charged particles and a solution containing negatively charged particles (here, the “solution containing charged particles” refers to not only a solution of a polymer or a monomer, but also This includes a wide range of solutions containing charged particles such as the micelle aqueous solution described above.) The method of forming an alternately adsorbed film by alternately immersing the film-forming material in these solutions is widely used. It is possible to use.

 According to an experiment conducted by the inventor of the present application, it has been found that the formation of micelles can be promoted by applying ultrasonic waves to the aqueous solution. Therefore, when forming an alternate adsorption film using a micelle solution, it is preferable to apply ultrasonic waves to a tank containing the micelle solution. The ultrasonic generator 70 in the apparatus for manufacturing an alternately adsorbed film shown in FIG. 7 is a device for applying ultrasonic vibration to the first tank 100 or the second tank 200. If the ultrasonic generator 70 applies ultrasonic vibration to the tank containing the micelle solution, micelle formation is promoted. However, the ultrasonic generator 70 is not necessarily used only when a micelle solution is used, but can be widely used when a solution containing components that are difficult to uniformly disperse is used. In addition, depending on the solution, there are many cases where the components are easily dispersed uniformly by increasing the temperature. When such a solution is used, a heating device having a function of heating the solution in the tank may be added.

Finally, a unique method for imparting an initial surface charge to the surface of the substrate 10 will be described. In order to form an alternate adsorption film on the substrate 10, it is necessary to provide an initial surface charge as described above. For example, in the example shown in FIG. 2A, a negative initial charge is applied to the surface of the substrate 10. Such an initial surface charge can usually be provided by a method such as introducing a 〇H group into the surface by a chemical method.Here, a method of applying the initial surface charge by a physical method is described. I will tell you. This method can be used when at least the surface of the substrate 10 is made of a conductive material. Specifically, this method is effective when a metal or a semiconductor is used as the substrate 10. Further, in order to carry out this method, a counter electrode is provided in advance in the tank, and a voltage application unit for applying a voltage between the surface of the substrate 10 and the crystal unit 20 and the counter electrode is provided. Must be provided. FIG. 14 shows an example of an apparatus to which such components are added. A counter electrode 80 is provided in the storage tank 110 in advance. The counter electrode 80 is opposed to the surface (made of a conductive material) of the substrate 10 and the electrode 21 on the crystal unit 20 by the voltage application unit 90. A predetermined voltage can be applied between the electrode 80 and the electrode 80.

 In this example, the voltage applying unit 90 has a function of applying a voltage so that the substrate 10 and the crystal unit 20 side are negative and the counter electrode 80 side is positive. As a result, the surface of the substrate 10 and the crystal unit 20 , It is possible to give a negative initial charge. Therefore, when an alternately adsorbed film is formed using this apparatus, chemical treatment for giving an initial surface charge to the surfaces of the substrate 10 and the crystal unit 20 is not required.

 S 6. Specific Examples

 Here, specific examples performed by the inventor of the present application will be described.

<<< First Embodiment: >>>

First, poly-allylamine hydrochloride (abbreviation: PAH: molecular weight = 55000) is used as a positive electrolyte polymer to be placed in the storage tank 110 of the apparatus shown in FIG. As the negative electrolyte polymer, polyacrylic acid (abbreviation: PAA: molecular weight = 9000) was used. Both were yield capacity to create an aqueous solution of a concentration of 10_ ² mol / 1 in each vessel. In addition, ultrapure water of 18οΩ · οπι or more was prepared as pure water to be used for the rinsing bath.

As the substrate 10, a slide glass is used. After soaking for 1 hour in a solution in which hydrogen water was mixed at 7: 3, the resultant was soaked in a solution in which water, hydrogen peroxide solution and ammonium hydroxide were mixed in 5: 1: 1 for 30 minutes, and washed with pure water. Thereby, the surface of the substrate 10 can be subjected to hydrophilic treatment, and the surface can be negatively charged by introduction of OH_ groups. The charging is saturated. On the other hand, as the crystal resonator 20, a crystal resonator having characteristics of 10 MHz and AT cut was prepared. It has a disk shape with a diameter of 8.0 mm and a thickness of 100 zm, and disk-shaped gold electrodes with a diameter of 4.5 mm and a thickness of 0.3 zm are formed on both sides. The quartz oscillator 20 was washed with ethanol, immersed in an ethanol solution of mercaptopropionic acid at a concentration of 1 mol / 1, washed with ethanol again, further washed with pure water, and dried. Thereby, the surface of the crystal unit 20 can be subjected to the hydrophilic treatment, and the surface can be negatively charged by introducing the OH— group. The charging is still saturated.

 The substrate 10 and the crystal unit 20 thus prepared were introduced into the apparatus shown in FIG. 7, and film formation was started. The lifting timing from the storage tanks 110 and 210 is the timing when the amount of change in the frequency detected by the frequency detection unit 50 reaches a predetermined reference value f ref = 250 Hz. Rinsing baths in tanks 220, 230, and 240 were controlled so that they were immersed for 2 minutes, 1 minute, and 1 minute, respectively. As a result, an alternate adsorption film having a uniform film thickness as shown in FIG. 8 was formed. The thickness of each of the layers A and B was about 1 Onm.

 <<< Second embodiment >>>

In this example, a positively charged micelle solution was used as a solution containing positively charged particles to be put into the storage tank 110 of the apparatus shown in FIG. Specifically, dispersing barium Blow wells as Fuwerai preparative particles (BaFe ₁₂ 〇 _19), a and a surfactant Tsu also positive charge hydrophilic groups CT AB (Cethyltrimethyl Ammonium Bromide), it it water In this way, a micelle solution was prepared. Concentration of each component Is Bruno Riumuferai bets is ^{1 X 1 0- 4 mol / 1} , CTAB was set to be 1 x 1 0 one ³ mol / 1. When ultrasonic waves were applied to this aqueous solution, micelles whose surface was positively charged were formed as shown in FIG. On the other hand, an aqueous solution of polyacrylic acid having a concentration of 10 to ² mol / 1 was used as a solution containing negatively charged particles to be placed in the storage tank 210 (here, an aqueous solution of an electrolyte polymer). Other conditions are exactly the same as in the first embodiment described above. However, ultrasonic waves were always applied to the solution in the storage tank 110 so that the micelles were efficiently formed. Industrial availability

The alternate adsorption film according to the present invention can be used for light-emitting elements for displays of various electronic devices, various sensors, printed circuit boards, integrated circuits, optical waveguides, optical fibers, biomaterials such as contact lenses, surface coating, etc. It can be used in a wide range of fields. For example, in the structure shown in FIGS. 8 to 11, an ITO electrode is used as the substrate 10 on the left end, an aluminum electrode or the like is deposited on the surface of the thin film B on the right end, and a voltage is applied between the two electrodes. When light is applied, light is emitted from the side exposed surface of each layer made of a photoconductive material, so that these structures can be used as a light emitting element (EL element). In particular, in the structure shown in FIG. 10, if the layer composed of the thin film B is used as a light emitting layer and the layer composed of the thin film A is used as a transport layer or an insulating layer for electrons and holes, efficient operation is possible. A light-emitting element can be formed. In addition, various sensors can be realized by adding a circuit for measuring a change in electrical characteristics of these structural parts such as a photocurrent generated between the electrodes and an electric resistance between the electrodes. For example, if a photoconductive material is used as the thin film material constituting each layer, these structures can be used as an optical sensor. If a material whose electrical characteristics change due to heat is used, a thermal sensor can be used. Can be used as The structure shown in Fig. 9 and Fig. 11 In this case, the optical properties such as the refractive index are different between the surface portion and the deep portion, so that it is possible to form an optical waveguide such as an optical fiber or an optical lens, and further, the electrical resistance and the like between the surface portion and the deep portion. Since the electrical properties of these are also different, it is also possible to form printed circuit boards and wiring sections for integrated circuits. In addition, since the surfaces of these structures are charged, they have the property of adsorbing charged particles in the atmosphere. If this property is used, it can be used as a gas sensor or biosensor for detecting smoke or gas, or it can be used as a filter to adsorb and remove smoke or gas.

Claims

The scope of the claims

1. A method for producing an alternately adsorbed film having a multilayer structure by alternately immersing a film-forming material (10) several times in a solution containing positively charged particles and a solution containing negatively charged particles,

 When the film-forming material (10) is put in and taken out of each solution, the crystal oscillator (20) is put in and taken out at the same time, and the oscillation frequency of the crystal oscillator with respect to the point in the solution is set. A method for producing an alternately adsorbed film, wherein the film is taken out of the solution when the amount of change reaches a predetermined reference value fref or when the change speed V of the oscillation frequency reaches a predetermined reference value vref.

2. A method for producing an alternately adsorbed film having a multilayer structure by alternately immersing the film-forming material (10) several times in a solution containing positively charged particles and a solution containing negatively charged particles,

 When the film-forming material (10) is put in and taken out of each solution, the crystal unit (20) is put in and taken out at the same time, and the impedance change of the crystal unit based on the point in the solution. Manufacturing an alternately adsorbed membrane characterized in that the solution is released from the solution when the amount ΔΖ reaches a predetermined reference value Zref or when the rate of change of impedance Vz reaches a predetermined reference value Vzref. Method.

3. An apparatus used to manufacture a layer-by-layer alternate adsorption film by alternately immersing the film-forming material (10) several times in a solution containing positively charged particles and a solution containing negatively charged particles. And

A first tank (100) for containing a solution containing positively charged particles, a second tank (200) for containing a solution containing negatively charged particles, and a material (10) for forming a film. A robot arm (30) for holding, The film-forming material (10) alternates between a state of being immersed in the solution in the first tank (100) and a state of being immersed in the solution of the second tank (200). A crystal arm attached to the robot arm (30) so as to be immersed in each solution together with the robot arm driving section (40) for driving the robot arm (30) and the material for film formation (10). Vibrator (20),

 A frequency detecting section (50) for detecting an oscillation frequency of the quartz oscillator (20); and a film forming section for controlling the robot arm driving section (40) based on the frequency detected by the frequency detecting section (50). Control unit (60),

 An apparatus for manufacturing an alternate adsorption film, comprising:

4. In the apparatus for manufacturing an alternate adsorption film according to claim 3,

 An apparatus for manufacturing an alternate adsorption film, further comprising an ultrasonic generator (70) for applying ultrasonic vibration to a solution contained in a tank.

5. In the apparatus for manufacturing an alternate adsorption film according to claim 3,

 A counter electrode (80) that can be immersed in the solution in the bath;

 A voltage applying unit (90) for applying a voltage between the film-forming material (10) and the quartz oscillator (20) and the counter electrode (80);

 An apparatus for producing an alternately adsorbed film, further comprising:

6. The alternately adsorbed film formed by alternately immersing the film-forming material (10) several times in a solution containing the first charged particles and a solution containing the second charged particles having different electrical polarities is formed. A structure having

A structure having an alternately adsorbing film, wherein the thickness of each layer (A, B) of the alternately adsorbing film monotonically increases or decreases as going from a deep portion to a surface.

7. An alternate adsorption film formed by alternately immersing the film-forming material (10) a plurality of times in a solution containing first charged particles and a solution containing second charged particles having mutually different electrical polarities. A structure having

 The thickness of the layer containing the first charged particles (A) is adjusted so that the physical properties of the second charged particles are dominant in the entire layer of the alternating adsorption film. A structure having an alternately adsorbed film, which is sufficiently smaller than the film thickness of (B).

8. Alternating adsorption film formed by alternately immersing the film-forming material (10) several times in a solution containing the first charged particles and a solution containing the second charged particles having different electric polarities. A structure having

 The thickness of each layer (A) containing the first charged particles monotonically decreases as going from the depth to the surface, and the thickness of each layer (B) containing the second charged particles monotonically goes from the depth to the surface. A structure having an alternating adsorption film characterized by increasing.

9. By alternately immersing the film-forming material (10) several times in the first liquid containing positively charged particles and the second liquid containing negatively charged particles, an alternately adsorbed film having a multilayer structure is formed. In the method of manufacturing,

 By wrapping uncharged particles or particles that have only an insufficient charge to perform alternate adsorption with a plurality of charged molecules, a sufficient charge to perform alternate adsorption as a whole is obtained. Characterized by using charged liquid particles formed in the liquid and dispersing the charged particles in the liquid as one or both of the first liquid and the second liquid. Manufacturing method of membrane.

10. The method for producing an alternate adsorption film according to claim 9,

Disperse ferrite fine particles or metal complex fine particles and surfactant in water. And thereby forming micelles in which the fine particles are wrapped around the surfactant molecules, and using the micelles as charged particles.