KR20040046426A - Methed for preparing polyaniline thin film using a cluster beam deposition apparatus - Google Patents

Abstract

PURPOSE: A method for making a polyaniline thin film by using a cluster beam deposition device is provided to obtain a polyaniline film having a uniform thickness, excellent surface roughness and a long work life is obtained. CONSTITUTION: The method for making a polyaniline thin film by using a cluster beam deposition device comprises the steps of: heating a crucible(12) containing polyaniline emeraldine base having average molecular weight of 5,000-130,000 by applying a certain electric voltage to vaporize the base; forming clusters by passing the polyaniline vapor through a nozzle disposed over the crucible(12); and depositing the polyaniline vapor on the substrate(1) at room temperature, the substrate(1) being put to earth, to produce polyaniline in a reduced form.

Description

Method for preparing polyaniline thin film using cluster beam deposition apparatus {Methed for preparing polyaniline thin film using a cluster beam deposition apparatus}

The present invention relates to a method for producing a polyaniline thin film using a cluster beam deposition apparatus, and more particularly to a method for producing a polyaniline thin film having a small surface roughness and a uniform thickness.

Conductive polymers are materials that have both electrical, magnetic and optical properties of metals and mechanical properties and processability of polymers. They are light, flexible, and freely regulated in electrical conductivity and electronic state. Rather, it can be applied in various forms to special application surfaces that were not feasible before. In general, a conductive polymer has a chain structure in which a single bond and a double bond of carbon atoms are alternately repeated, so that the pi electrons can move freely to a certain extent, it is called a pi conjugated polymer. Doping these polymers by chemical or electrochemical methods is also called synthetic metals because they can control the conductivity from the insulator to the metal.

As described above, the pie conjugated polymer material has advantages of plastic and properties as a metal or a semiconductor, and typical conductive polymers include polyacetylene (PA), polyaniline (PANI), and polypyrrole (Ppy). Polyacetylene, a conductive polymer material synthesized at the beginning, has a high direct current conductivity (~ 105 S / cm), but is not stable to air and heat, and is not easy to synthesize and process.However, polyaniline or polypyrrole is stable in air. Due to its excellent processability, transistors, photodiodes, and light emitting diodes (LEDs) using these conductive polymers are currently being studied. In particular, polyaniline has a high yield from relatively inexpensive monomers. It can be easily synthesized and has the advantage of providing conductivity relatively easily through protonation doping or oxidation doping. Such a polyaniline thin film can be mainly produced by spin coating, but like other conductive polymers, the expression of the polyaniline's conductivity is due to π-electron delocalization along the polymer chain, so that its molecular chain is rigid, solubility is achieved. There is a problem that it is difficult to obtain a uniform thin film.

Therefore, US Pat. Nos. 5,100,977, 5,560,870, 5,776,659 and the like introduce polyaryline by introducing a substituent into the polyaniline backbone by copolymerizing N-alkyl aniline and aniline or sulfonating polyaniline to increase the solubility of polyaniline. A method of increasing the flexibility of the molecular chain by reducing the π-conjugation has been proposed. However, the conductive polyaniline prepared by this method has a problem in that the solubility is improved but the electrical conductivity decreases as the π-conjugation is reduced. In addition, a conductive polyaniline that can be dissolved in a polar organic solvent can be prepared using a protonic acid dopant such as dodecyl benzenesulfonic acid, camphorsulfonic acid, or paratoluenesulfonic acid, but it is difficult to industrially use due to insufficient physical properties such as solubility and conductivity. It is true.

As described above, even if the solubility is increased by introducing a functional group into the polyaniline, or the solubility in the organic solvent is increased by selecting an appropriate organic solvent, the following problems occur when using a wet method such as spin coating.

In the manufacture of an electroluminescent device display, a conductive polymer layer and a buffer layer are added between an electrode and an electroluminescent device. Thus, when forming a multilayer coating film having a different composition, when the dissolution characteristics of each layer are the same, the upper and lower portions are rotated during the spin coating process. The dissolution or swelling of each other at the interface of the layer forms a mixed-layer, thereby reducing the efficiency. Therefore, the solvent of the conductive polymer layer has a limitation that must be selected so as not to dissolve the buffer layer. In addition, after the wet coating, the solvent must be removed by drying at a high temperature and high vacuum, and it is very difficult to completely remove even a small amount of solvent molecules stuck in the polymer chain. Since the solvent molecules remaining in the polymer membrane are physically bonded to the polymer chain by only weak intermolecular force, when the device is driven out, the solvent molecules have a fatal adverse effect on the life of the device. In addition, in the case of wet coating, it is difficult to control the thickness of the surface and defects such as uncoated parts are present on the surface. There is a disadvantage that the driving efficiency of the deterioration.

In addition, when manufacturing the polymer thin film by PVD, not only it is difficult to vaporize the polymer, but also has a disadvantage that the roughness of the thin film is very poor since the polymer is vaporized and the generated radical prepolymers do not have orientation.

Meanwhile, Korean Patent No. 10-252782 discloses an emeraldine base by vaporizing aniline monomer, ammonium sulfate, and hydrochloride through an improved chemical vapor deposition (CVD) method to improve the disadvantages of the wet coating method. A method of making a polyaniline thin film in form is disclosed, but nothing is disclosed that can demonstrate that a thin film in the form of an emeraldine base has been produced. Since the aniline monomer is a liquid, it is difficult to control the amount of vapor during vapor deposition, and when the polyaniline is formed by radical polymerization between the aniline monomers, it reacts randomly such as reacting with the ortho position as well as the para position of other anilines. The sharp decrease in π-conjugation leads to a very poor electrical conductivity, especially because of their high probability of being unpolymerized and present as monomeric unreacted or dimer by-products, which are critical to the device's performance. There is this. In addition, when the polymer film is manufactured by the chemical vapor deposition method, there is a problem in that it is difficult to produce a multilayer thin film due to very poor surface roughness.

Therefore, the technical problem to be achieved by the present invention is to overcome the problems of the prior art to provide a method for producing a polyaniline thin film excellent in electrical properties with a uniform surface and almost no defects without a solvent effect.

1 is an internal photograph of a cluster beam deposition apparatus used in the present invention.

2 is a schematic diagram of a cluster beam deposition apparatus used in the present invention.

3 shows the FT-IR spectra of polyaniline pellets having a weight average molecular weight of 5000 and polyaniline thin films prepared according to Examples 1 and 4 of the present invention.

4 (a) shows the XPS spectrum of a polyaniline pellet having a weight average molecular weight of 5000.

Figure 4 (b) shows the XPS spectrum of the polyaniline thin film prepared by Example 1 of the present invention.

Figure 4 (c) shows the XPS spectrum of the polyaniline thin film prepared by Example 4 of the present invention.

Figure 5 shows the FT-IR spectrum of the polyaniline thin film prepared by Example 3 of the present invention.

Figure 6 shows the FT-IR spectrum of the polyaniline thin film prepared by Example 6 of the present invention.

Figure 7 shows the FT-IR spectrum of the polyaniline thin film prepared by Comparative Example 1 of the present invention.

8 shows the FT-IR spectrum of the polyaniline thin film prepared by Comparative Example 2 of the present invention.

9 is a SEM photograph of the polyaniline thin film prepared according to Example 4 of the present invention.

10 is a SEM photograph of the polyaniline thin film prepared according to Example 5 of the present invention.

11 is an AFM photograph of a polyaniline thin film prepared according to Example 4 of the present invention.

12 is an AFM photograph of a polyaniline thin film prepared according to Example 5 of the present invention.

FIG. 13 is an AFM photograph of a polyaniline thin film prepared by Comparative Example 3.

<Description of the symbols for the main parts of the drawings>

1: board 2: monitor

3: ammeter 4: shutter

5: variable voltage circuit 6: cluster

7: acceleration electrode 8: grid

9: filament 10, 11: variable voltage

12: Crucible 13: Thermocouple

14: support

The present invention to achieve the above technical problem

Vaporizing the polyaniline by heating the crucible 12 containing the polyaniline emeraldine base having a weight average molecular weight of 5000 to 130,000 by voltage application;

Passing the polyaniline vapor through a nozzle above the crucible (12) to form a cluster; And

It provides a polyaniline thin film manufacturing method using a cluster beam deposition apparatus comprising the step of forming a polyaniline in the reduced state of the polyaniline vapor is deposited on the grounded substrate (1).

According to one embodiment of the present invention, it is preferable that the temperature of the crucible 12 is 300 to 350 ° C.

In addition, the deposition rate is preferably 0.6 ~ 0.8 Pa / S.

It is also preferable not to heat the substrate 1.

Meanwhile, the polyaniline produced on the substrate 1 may be in the form of protoemeraldine base (PEB).

According to another embodiment of the present invention, it is preferable that the polyaniline cluster is further ionized by an ionization device provided on the crucible 12.

According to a preferred embodiment of the present invention, the ionizer comprises: a circular grid 8 surrounding a portion through which the cluster passes; An electron emission filament 9 surrounding the circular grid 8 in an octagonal surface; It is preferable to include an ion accelerating electrode 7 located above the circular grid 8 and grounded.

Meanwhile, the polyaniline produced on the substrate 1 may be in the form of Leucoemeraldine Base (PEB).

Hereinafter, the present invention will be described in more detail.

Polyaniline may be selected from (a) Leucoemeraldine Base (LEB), (b) Protoemeraldine Base (PEB), (c) according to the proportion of imines present in the main chain, as shown in the following Chemical Formula 1 ) There are five oxidation states: Emeraldine Base (EB), (d) Nigraniline (NA), and (e) Pernigraniline (PNA).

(a) Leucoemeraldine Base (LEB): 1-Y = 0

(b) Protoemeraldine Base (PEB): 1-Y = 0.25

(c) Emeraldine Base (EB): 1-Y = 0.5

(d) Nigraniline (NA): 1-Y = 0.75

(e) pernigraniline (PNA): 1-Y = 1.0

In the present invention, when the cluster beam is not ionized, a polyaniline thin film in the form of protomeraldine is obtained, and when the cluster beam is ionized using an ionizer, a polyaniline thin film in the form of a leucomeraldine base may be obtained. .

In the method for producing a polyaniline thin film according to the present invention, it is preferable to use polyaniline in the form of an emeraldine base having a weight average molecular weight of 5000 to 130,000. If the weight average molecular weight is less than 5000, the roughness of the formed thin film may be deteriorated, and it is not preferable because the conductivity may be reduced, and if it exceeds 130,000, it is preferable because it is difficult to vaporize the polymer. Not. The reason why the roughness of the thin film formed when using polyaniline whose weight average molecular weight is less than 5000 is used is as follows. When the polymer is heated, the polymer decomposes to form a radical free polymer. The free polymer generated when heating less than 5000 polyaniline has a low degree of polymerization because of the small number of repeating units, and a polymer backbone having low polymerization degree. This is because another polymer main chain may be randomly stacked on top of the film, resulting in an uneven thin film. The reason why the conductivity decreases is that, as described above, not only the low degree of polymerization of the polymer but also the small number of repeating units of the prepolymer may react to the ortho position of the aniline ring of other reacting free polymers. This is because the sharp decrease.

At this time, the organic molecules in the vapor state passes through the nozzle located on the cover of the crucible 12, thereby forming clusters due to intermolecular collisions, and have a directional beam shape. According to the conventional chemical vapor deposition (CVD) method, since the aniline monomer to be deposited is deposited separately, the surface has a rough island shape. In the case of cluster beam deposition, a cluster combined with a weak dispersion force is a substrate. Since it is broken when colliding with and stacked evenly on the substrate, there is an advantage that a thin film having an even surface is formed. The advantage of using the cluster beam is the high directionality and the translational kinetic energy of the beam obtained when the gas molecules are adiabaticly expanded in a high vacuum state.

On the other hand, the temperature of the crucible 12 of the cluster beam deposition apparatus used in the production of the polyaniline thin film according to the present invention is preferably 300 to 350 ° C. If the temperature is less than 300 ° C, the polymer is difficult to vaporize, and the polyaniline thin film is difficult to form because it cannot supply sufficient energy necessary for thermal polymerization to occur in the substrate 1, and if the temperature exceeds 350 ° C, it is unstable. Since the prepolymer radical of is formed, the chemical composition of the material forming the thin film may not be polyaniline and the surface roughness is also poor, which is not preferable.

In addition, the deposition rate in the cluster beam deposition according to the present invention is preferably from 0.6 to 0.8 Å / S, when the deposition rate is less than 0.6 때문에 because the deposition rate of the thin film is too slow, it is difficult to form a polymer thin film properly and 0.8 Å If it exceeds, there is a disadvantage that the roughness of the produced polymer thin film is poor, which is not preferable. The deposition rate depends on the weight average molecular weight of the polymer to be placed inside the crucible and can be controlled by the temperature of the crucible, but can also be controlled using an ionized cluster beam deposition apparatus described below.

It is preferable not to heat the substrate 1 at the time of cluster beam deposition. This is because the vaporized prepolymer condenses and thermal polymerization occurs because heating the substrate 1 makes the prepolymer difficult to condense and undesirable for thin film formation.

The polyaniline thin film thus prepared is not a fully reduced form but is in a reduced form than the emeraldine base form and is in the form of protomeraldine, which will be described in detail in the following Test Example. The polyaniline thin film of the protomeraldine type thus formed may be controlled to an emeraldine base form by a known method such as hydrogenation-deprotonation or oxidation in air.

In the present invention, it is preferable to further include the step of ionizing the polyaniline cluster by the ionizer provided on the top of the crucible 12, in order to make a thinner even surface. The ionizer comprises a circular grid (8) surrounding a portion through which the cluster passes; An electron emission filament 9 surrounding the circular grid 8 in an octagonal surface; It is preferable to include an ion accelerating electrode 7 located above the circular grid 8 and grounded. As such, the cluster is ionized with a cation and then accelerated by its repulsive force by applying a positive voltage to the base. In the case of using the ionized cluster beam, the amount and energy of the cluster beam can be changed by adjusting electrical factors such as the ionization voltage, the acceleration voltage, and the current density of the cluster beam, thereby forming a more uniform thin film. have.

1 is an internal photograph of a cluster beam deposition apparatus used in the present invention. Unlike the conventional metal beam or inorganic vapor deposition cluster beam deposition apparatus, the secondary circuit is very simple and the device is very simple as a whole it can be seen that easy to manufacture.

2 is a schematic diagram of a cluster beam deposition apparatus used in the present invention.

The material of the substrate 1 is a copper alloy and is a large substrate having a size of 70 mm x 70 mm x 1 mm, which is provided with a heating device but is not used for the deposition of polyaniline according to the present invention. The thin film thickness monitor 2 represents the deposition rate and the thickness of the deposit in Å / s and kÅ units, respectively, to monitor the thickness of the thin film and to adjust the appropriate thickness. Since the ammeter 3 is connected to the substrate 1 and grounded, the voltage of the substrate is 0V, unlike the application of a negative voltage to the substrate in the prior art. Thus, the circuit is simplified, and there is no temperature rise by applying a voltage, so there is no fear of disassembling again after the polyaniline thin film is deposited. On the other hand, the degree of ionization of the cluster 6 can be quantitatively determined by the ammeter 3. The shutter 4 is provided to be opened and closed from the outside and is initially closed, and is provided to be rotated from the outside when a constant deposition rate is reached to prevent deposition of unpurified impurities. The variable voltage circuit 5 is connected to apply a voltage to the crucible 12 to form a potential difference with the substrate, and the terminal thereof is grounded. The ion accelerating electrode 7 is a donut-shaped stainless steel plate which is grounded and is similar to the base (substrate), and is 0V, and shortens the distance from the substrate, thereby rapidly accelerating the cluster ions 6. The grid 8 serves as an anode that pulls the electron beam emitted from the filament 9 to the center, and unlike the conventional device, since the grid 8 is designed in a circular shape, the grid 8 can be effectively ionized, and the electron density is also known. Higher than the device. The electron emitting filament 9 serves as a cathode for releasing hot electrons, and is surrounded by octagonal surfaces around the grid 8. The variable voltage regulator 10 is for applying a positive voltage to the grid 8 and the variable voltage generator 11 is for flowing a current to the filament 9 to emit hot electrons. The material of the crucible 12 uses stainless steel because the heat transfer is good and the processing is easy and hard. They also use better graphite, which is better heat transfer and lighter than stainless steel. The crucible 12 may contain deposits, and the upper cover includes a nozzle having a diameter of 1 mm and a depth of 1 mm to form a cluster. A thermocouple 13 is provided for measuring the temperature of the crucible 12 from the voltage difference between the measurement line and the correction line (K-type). The support 14 is made of heat-resistant alumina as a support for fixing the crucible 12 and the ionization part, that is, the grid 8 and the filament 9.

The polyaniline thin film deposited using the ionizer may be in the form of a leuco emeraldine base as a reduced form more than the proto emeraldine form, which will be described in detail in the following test examples.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention, but the present invention is not limited thereto.

Example 1

0.06 g of powder of polyaniline (manufactured by Aldrich) in the form of an emeraldine base having a weight average molecular weight of 5000 was placed in a graphite crucible, and a voltage was applied to a tungsten wire surrounding the outside of the crucible, so that the temperature inside the crucible was 300 ° C. Heated to 10 ⁻⁵ Torr. At this time, the shutter was opened to generate a cluster beam, and the deposition rate was adjusted to 0.7 kW / S, and the film was deposited for 20 minutes to prepare a polyaniline thin film.

Example 2

A polyaniline thin film was prepared in the same manner as in Example 1, except that polyaniline in the form of an emeraldine base having a weight average molecular weight of 65,000 was used.

Example 3

A polyaniline thin film was prepared in the same manner as in Example 1, except that polyaniline in the form of an emeraldine base having a weight average molecular weight of 130,000 was used and the temperature of the crucible was 350 ° C.

Example 4

A polyaniline thin film was prepared in the same manner as in Example 1 except that the cluster beam was ionized using the ionizer 20.

Example 5

A polyaniline thin film was manufactured in the same manner as in Example 2, except that the cluster beam was ionized using the ionizer 20.

Example 6

A polyaniline thin film was manufactured in the same manner as in Example 3, except that the cluster beam was ionized using the ionizer 20.

Comparative Example 1

A polyaniline thin film was prepared in the same manner as in Example 1 except that polyaniline in the form of an emeraldine base having a molecular weight of 130,000 was used and the temperature inside the crucible was 250 ° C.

Comparative Example 2

A polyaniline thin film was manufactured in the same manner as in Comparative Example 1, except that the temperature of the crucible was 400 ° C.

Comparative Example 3

0.2 g of polyaniline in the form of an emeraldine base having a weight average molecular weight of 65,000 was dissolved in 10 ml of NMP solution and stirred for 24 hours. After filtering the solution with a filter filter, a glass substrate was mounted on the sample holder of the spin coating apparatus, 140 μl of the polyaniline solution was dropped in the central portion, spin coated, and dried in a vacuum oven for 30 minutes to prepare a polyaniline thin film.

Test Example 1

Analysis of FT-IR Spectrum

Using the infrared absorption spectrum, the chemical composition of the polyaniline thin film prepared according to Examples 1 and 4 was confirmed and shown in FIG. 3. In this case, KBr pellets were used as the substrate to obtain infrared absorption spectra. The original sample, polyaniline in the form of an emeraldine base, has five strong absorption bands, 833, 1166, 1306, 1503 and 1593 cm ⁻¹ , and the main peaks of the thin films prepared in Examples 1 and 4 coincide. It can be seen that the deposited thin film is polyaniline. However, the intensity of the quinoid diimine peak appearing near 1166 cm ⁻¹ is greatly reduced, indicating that the deposited thin film is more reduced than the emeraldine base form. The reason why the reduced thin film is formed is that as the number of imine groups in the polyaniline molecule becomes thermodynamically stable, it can be changed to the most stable form when sufficient energy required for thermal polymerization is applied.

Meanwhile, the chemical compositions of the polyaniline thin films prepared according to Examples 3 and 6 of the present invention and the thin films prepared by Comparative Examples 1 and 2 are shown in FIGS. 5 to 8 by analyzing an infrared spectrum. FIG. 5 is an infrared spectrum of the polyaniline thin film prepared by Example 3, and FIG. 6 is an infrared spectrum of the polyaniline thin film prepared using the ionizer according to Example 6. FIG. The spectra all have peaks of 833, 1166, 1306, 1503 and 1593 cm ⁻¹ , indicating that a polyaniline thin film was formed. On the contrary, in the case of FIG. 7, which is a spectrum of the thin film prepared by Comparative Example 1, no characteristic peak of the polyaniline thin film is shown, and it is understood that the deposited material is not polyaniline. This is because the polymerization did not occur properly in the substrate because the temperature required for thermal polymerization is not sufficient.

Meanwhile, FIG. 8 is a spectrum of Comparative Example 2 in which the temperature of the crucible is 400 ° C., and the positions of characteristic peaks are slightly shifted as 821.6, 1172.6, 1300, 1508.2, and 1597, and compared with FIG. 5. The intensity of the 3030 cm ⁻¹ peak increases, which corresponds to the CH stretching of the aromatic ring, which corresponds to a peak that is not apparent in the polyaniline thin film. Thus, it can be seen that the polyaniline thin film was not properly formed.

Test Example 2

Analysis by X-ray Photoelectron Spectroscopy (XPS)

Through the XPS spectrum of the N1s cabinet level, the polyaniline thin films prepared in Examples 1 and 4 were analyzed and the results are shown in FIG. 4. The spectra of polyaniline are separated into four peaks of 398.63, 399.74, 400.85, and 402.74 eV, respectively, in order of neutral imine, neutral amine, oxidized amine, and hydrogen bound imine, respectively. The binding energy for protonated imine is shown. Figure 4 (a) is the spectrum of the emeraldine base pellets, compared with that in the case of Figure 4 (b) which is a spectrum for Example 2 compared to the more reduced state than the emeraldine base form It can be seen, but because it is not a fully reduced state, it can be seen that it is close to the form of Protoemeraldine Base (PEB). In addition, in the case of FIG. 4 (c), which is the spectrum of Example 4, it can be seen that the state is almost completely reduced to a leuco emeraldine base form.

Test Example 3

Scanning Electron Microscopy (SEM)

SEM measurements were performed on the polyaniline thin films prepared in Examples 4 and 5, which are shown in FIGS. 9 and 10. It can be seen that the polyaniline thin film produced according to the present invention is suitable for electronic devices because of its uniformity and very low defect. On the other hand, as the weight average molecular weight of polyaniline increases, the surface becomes more uniform and roughness is excellent.

Test Example 4

Atomic Force Microscopy (AFM)

The roughness of the surface can be known through atomic force microscopy (AFM). The AFM allows the silicon probe to scan the surface of the thin film and present an image of the surface, numerically indicating the roughness from the baseline. AFM was measured for the polyaniline thin films prepared in Examples 4 to 5 and Comparative Example 3, and the results are shown in FIGS. 11 to 13. In the case of Comparative Example 3 prepared by spin coating, a polyaniline thin film prepared according to the present invention has a large number of defects such as a portion where polyaniline is not coated and a portion that remains in a lump without being dissolved in a solvent. In this case, it can be seen that there is almost no defect on the surface and a very uniform thin film is obtained. As the weight average molecular weight increases, the roughness is excellent and the thin film is uniform.

According to the present invention, a reduced thickness of the polyaniline thin film may be manufactured by a simple process, and the polyaniline thin film prepared according to the present invention may have a uniform thickness and a thickness than that of the polyaniline thin film prepared by conventional spin coating or vapor deposition. Since there is no effect, it is suitable for the manufacture of multilayer thin films and can improve the performance of electronic devices. In addition, since there is no solvent effect that may occur in the thin film by spin coating, the life of the device can be extended, and the electrical properties are greatly improved by a simple doping process, and thus it can be very usefully applied to the device.

Claims (8)

Vaporizing the polyaniline by heating the crucible 12 containing the polyaniline emeraldine base having a weight average molecular weight of 5000 to 130,000 by voltage application; Passing the polyaniline vapor through a nozzle above the crucible (12) to form a cluster; And The polyaniline vapor is deposited on a grounded room temperature substrate (1) to form polyaniline in reduced form. Polyaniline thin film manufacturing method using a cluster beam deposition apparatus comprising a. The method of manufacturing polyaniline thin film using a cluster beam deposition apparatus according to claim 1, wherein the temperature of the crucible (12) is 300 to 350 ° C. The method of claim 1, wherein the deposition rate is 0.6 to 0.8 Å / S polyaniline thin film manufacturing method using a cluster beam deposition apparatus. 2. The method for producing a polyaniline thin film according to claim 1, wherein the substrate (1) is not heated. The method of claim 1, wherein the polyaniline produced on the substrate (1) is a polyaniline thin film manufacturing method using a cluster beam deposition apparatus, characterized in that the form of Protoemeraldine Base (PEB). The method of claim 1, further comprising the step of ionizing the polyaniline cluster by an ionization device provided on the crucible (12). 7. An ionization apparatus according to claim 6, wherein the ionizer comprises: a circular grid (8) surrounding a portion through which the cluster passes; An electron emission filament 9 surrounding the circular grid 8 in an octagonal surface; Method for producing a polyaniline thin film using a cluster beam deposition apparatus, characterized in that it comprises an ion acceleration electrode (7) which is located above the circular grid and grounded. The method of claim 6, wherein the polyaniline produced on the substrate (1) is a polyaniline thin film manufacturing method using a cluster beam deposition apparatus, characterized in that the form of Leucoemeraldine Base (PEB).