KR100327105B1 - High luminance-phosphor and method for fabricating the same - Google Patents

Abstract

The present invention provides a method for forming a PbX (X = S or Se) thin film using atomic layer deposition or chemical vapor deposition and CaS, CaSe, SrS, SrSe, ZnS, ZnSe, BaS, BaSe, MgS, The present invention relates to a method for producing a phosphor by adding PbX (X = S, Se) to an MgSe parent material. The present invention uses a Pb-precursor that exhibits specific reaction characteristics as a reaction material. As the Pb-precursor, tetraalkyl (alkyl = methyl, ethyl, propyl, cyclohexyl, isopropyl) lead or tetra-aryl lead ( An organometallic compound such as tetraaryl lead) is used, and reacted with H ₂ X (X = S or Se) to deposit a very uniform PbX (X = S, Se) thin film by atomic layer deposition or chemical vapor deposition. In addition, the present invention is Pb by performing the deposition so that any one of CaS, CaSe, SrS, SrSe, ZnS, ZnSe, BaS, BaSe, MgS or MgSe or a mixed base material and PbX (X = S, Se) is a constant ratio It is a method of growing a phosphor thin film while adjusting the concentration. In particular, the present invention produces a phosphor having excellent color purity by selectively adding Pb ²⁺ ions to a parent material in a specific state during the manufacture of a phosphor, and a phosphor having excellent color and brightness while including Pb ²⁺ in a wide concentration range. It is.

Description

High luminance phosphor and method for manufacturing the same {High luminance-phosphor and method for fabricating the same}

The present invention relates to a PbS or PbSe thin film using a precursor having a specific reactivity, hereinafter referred to as PbX (X = S or Se) thin film, and also includes Pb ²⁺ ions as emission center ions, ^The present invention relates to a phosphor having a feature of selectively generating ²⁺ ions in a specific state and selectively generating only light corresponding to the state, an electroluminescent device having the phosphor, and a method of manufacturing the same.

In general, PbX (X = S or Se) thin films are usefully used in phosphors, solar cells, infrared detectors, and the like of electroluminescent devices. It looks at the PbX (X = S or Se) thin film formation method and its problems according to the prior art.

Until now, PbX (X = S, Se) is grown by atomic layer deposition, chemical vapor deposition, etc., and PbX (X = S or Se) is an ionic solid in which Pb ²⁺ and X ^2- are bonded. Coordination compounds that maintain the binding of Pb (thd) ₂ (thd = 2,2 ', 6,6'-tetramethyl -3,5-heptandionate), Pb (dedtc) ₂ (dedtc = diethyldithiocarbamate) have used the, or PbCl _2, halide and H ₂ S or H ₂ reaction system is PbS are grown to Pb (dedtc) ₂ decomposition, including the reaction used or S with Se such as PbBr _2. (U.S. Pat. 5496597, Registered Date June 20, 1994)

However, coordination compounds such as thd-compounds showed very non-uniform and poor reproducible growth characteristics. Halogen compounds have the disadvantage that halogen ions remain in the thin film or on the surface, which adversely affects the device manufacturing process and characteristics. It did not show good luminescence properties. In particular, in the case of Pb (thd) ₂ , oxygen, which is one of the precursor components, is added to the thin film to rapidly decrease the luminance.

Another prior art method for producing a PbS thin film is a method of reacting tetraethyl lead with a block copolymer matrix to form an active site and then flowing H ₂ S. In this case, PbS in the form of a nanocluster (nanocluster) is synthesized. At this time, the polymer used is regenerated by the reaction with H ₂ S, so the reaction proceeds repeatedly to increase the size of the cluster. This method cannot be used to deposit uniform PbS thin films and phosphor thin films.

In another conventional PbX (X = S, Se) thin film manufacturing method, a method of depositing monocrystalline metal oxides and sulfides on a single crystal substrate using an organometallic compound at a very low temperature (US Patent No. 4463426, 1985). 2. 8), which is a method of depositing sulfides and oxides by reacting alkyl, alkoxy, or halide compounds with oxygen or sulfur in the radical state. It is characterized in that the use of the light source to generate oxygen and sulfur in the radical state, but this is the main purpose of the thin film growth at low temperature.

On the other hand, when a transition metal element, a rare earth metal element, or the like is added as the emission center ion in the group II-VI compound parent material, it can be used as a phosphor that emits light in the red, blue, and green visible region. First, the general characteristics of the phosphor and the prior art of manufacturing such a phosphor thin film and their problems will be described.

There may be a variety of mechanisms in which phosphors emit light. First, in the case of an electroluminescent device, when an electric field is applied, electrons are injected into the phosphor from an interface between the phosphor and the insulating layer, and the accelerated electrons collide with the emission center ions in the phosphor, and electrons are excited to the ground state at the excited energy level. Will return as much energy as the energy difference between the two energy levels. In the case of a field emission display, light is emitted through a process of exciting collisions of electrons emitted from an electron tip or a thin film electron source into a fluorescent layer by exciting the emission center ions in the fluorescent layer. This principle of luminescence is called cathodoluminescence (CL). The photoluminescence (PL) phenomenon corresponds to the case where the energy source for exciting the emission center ion is light, not electrons. Phosphors that emit bright light through this phenomenon are used for information displays, that is, displays.

An electroluminescent device, a type of display, has many advantages such as high environmental resistance (vibration resistance, shock resistance), wide temperature range available, wide viewing angle, and fast response time. Have. However, although the brightness of red and green is very bright, the brightness of blue is low and there is a limit in that it cannot implement full-color of excellent quality. In the energy transition process for blue light emission, blue has a short wavelength, that is, the transition energy is large, which may be influenced more by the energy level due to impurities or unwanted chemical states.

In addition, the display device requires the development of high purity green and red phosphors together with high purity blue according to the application purpose, but there is a limitation in manufacturing such high brightness and high color purity phosphors in the prior art.

In general, in the field of blue electroluminescent devices, a thin phosphor of ZnS: Tm (a compound in which Tm is added to ZnS) has been studied for several decades, but shows only a low luminance of less than 1 cd / m ² at a driving frequency of 1 kHz. It was. Blue phosphors, unlike red and green phosphors, have a very low luminance and have been considered the biggest technical challenge in this field.

Recently, CaGa ₂ S _4, SrGa ₂ S ₄ as gallium sulfide fluorescent material, such as could be obtained a luminance of 12 cd / m ² under about 60Hz driving frequency. However, in the case of gallium sulfide, when grown by atomic layer deposition, gallium (Ga) does not have an appropriate chemical bonding state and cannot be grown by atomic layer deposition, and the price of Ga raw material is very expensive.

The growth of Pb-doped CaS fluorescent film, or CaS: Pb fluorescent film, was reported by Finnish E. Nykanen and others at the 1992 Electroluminescence Workshop (May 1, 1992, PP 199). As a precursor of Pb, a coordination compound such as Pb (thd) ₂ and Pb (dedtc) ₂ having a Pb + 2 (II) bond state and a halogen compound were used, and the characteristics of the electroluminescent device was 2.5 at 300 Hz driving frequency. As cd / m ² , it was very inferior to the performance of the electroluminescent device manufactured in the present invention. Ultraviolet rays were predominantly emitted under very low concentrations of Pb ²⁺ ions, UV and blue light emission were observed simultaneously at concentrations below 1.0 mol.%, And blue light emission was observed only at concentrations ranging from 1.0 to 1.5 mol.%. The best blue chromaticity was (0.13, 0.17). That is, as the concentration of Pb ²⁺ ion increased, the color changed continuously.

Another example of the growth of Pb-doped CaS as a fluorescent layer of an electroluminescent device is to produce a solid source material containing CaS and PbS or Pb metal and deposit it on a substrate by electron beam evaporation. (D. Poelman et al., J. Phys. D .: Appl. Phys. 30, 1997, 445). In this case, the characteristics of the fluorescent layer are very bad, and due to the clustering (clustering) of PbS has been reported to be insufficient to use as a blue phosphor. In this case, the luminance showed a value of 1 cd / m ² or less at 20 kHz driving frequency. This value corresponds to a very low luminance, considering the general tendency that the luminance increases with increasing driving frequency. In particular, it is reported that blue can be obtained only when the Pb ²⁺ ion concentration is 1.0 mol.% Or less due to the clustering tendency.

These inferior research results have been reported that the emission wavelength changes according to Pb concentration, and the luminance is very low at room temperature (300K) for SrS: Pb and SrSe: Pb (N. Yamashita et al., J. Phys. Soc. Japan, 53, 1984, pp. 419-426). Several devices have been proposed to mitigate the disadvantages of the techniques described above. One of them is described in SDI 99 DIGEST by the inventor of the present invention under the name "High-Luminanc Blue-Emitting CaS: Pb EL Device Fabrication Using Atomic Layer Deposition". This device, which is a high brightness blue light emitting CaS: Pb electroluminescent device, is fabricated using atomic layer deposition. Luminance L25 is 80 cd / m ² at a driving frequency of 60 Hz. The chart color coordinates in the range of (0.14, 0.07) to (0.15, 0.15) are almost the same as the blue chart color coordinates of the cathode ray tube. Another device is described by the inventor of the present invention in Asia Display 98 / IDRC under the name "Blue-Emitting Pb-doped Calcium Sulfide Electroluminescent Device Grown Using Tetraethyl Lead as Pb-Precursor". Blue-emitting CaS EL devices are grown using atomic layer epitaxy. In growing CaS: Pb, tetraethyl lead is first used as Pb precursor, which is a metal-organic compound that does not contain oxygen. These results show that CaS: Pb can be an excellent blue phosphor for bright full color EL devices. The EL spectrum shows intense peaks at a wavelength of 445 nm, showing pure blue emission. Unoptimized 3000ÅThickness CaS: Pb (0.3 at.%) Luminance, L60, is 32 cd / m ² at 1kHz frequency.

The PbX (X = S, Se) thin film according to the prior art as described above is not stable in uniformity and reactivity, the phosphor according to the prior art had a limit in implementing high brightness and high color purity, the present invention is It is designed to solve these problems and to meet all the requirements.

An object of the present invention is to provide a PbX (X = S, Se) thin film manufacturing method having a good thickness uniformity and stable reactivity.

Another object of the present invention is to provide a PbX (X = S, Se) thin film manufacturing method using a liquid precursor, the process cost is reduced in terms of material, time, manpower.

It is still another object of the present invention to provide a method of manufacturing a phosphor in which a process cost is reduced in terms of material, time, and manpower by using a liquid precursor.

Still another object of the present invention is to provide a phosphor of high brightness and high color purity and a method of manufacturing the same.

Still another object of the present invention is to provide an electroluminescent device having the phosphor and a method of manufacturing the same.

In order to achieve the above object, the present invention, in the preparation of PbX (X = S or Se) thin film, by using an organometallic compound Pb covalently bonded to a functional group as a Pb-precursor, the Pb-precursor and H ₂ X Reaction (X = S or Se) to form a PbX (X = S or Se) thin film, the PbX (X = S or Se) thin film is atomic layer deposition or chemical at a temperature of 150-500 ℃ It is preferable to grow and form by a vapor deposition method. As the Pb-precursor, tetra-alkyl lead having a tetravalent tetravalent bond with Pb, tetra-aryl lead or dicyclodipenta having a bivalent covalent bond with Pb is present. Dicyclodipentadienyl lead, bistrialkylsilyl lead may be used, and in the tetra-alkyl lead, tetra-aryl lead, alkylaryl lead, or bistrialkylsilyl lead, the alkyl group or aryl group may be methyl, methyl, At least one selected from ethyl, propyl, isopropyl, cyclohexyl, phenyl and benzyl groups.

Specifically, the method of forming PbX (X = S or Se) thin film of the present invention, which has been grown by using a precursor in the form of a covalent compound of +2 (II), has been shared with +4 (IV). Atomic layer deposition or chemical vapor deposition using organometallic compound precursors (eg, tetra-alkyl lead, tetra-aryl lead) and organometallic compound precursors (dicyclodipentadienyl) having a bivalent covalent bond This feature is characterized in that the thickness uniformity of the thin film is good and the reactivity is stable. In particular, the PbX (X = S or Se) thin film formation method of the present invention can obtain a very uniform PbX (X = S or Se) thin film on a large area substrate such as 12 "x 16".

Growth of quantitative PbX (X = S or Se) in the present invention was confirmed through the Rutherford backscattering spectrometry (RBS) analysis. RBS data showed that Pb and S had a composition ratio of about 1: 1. In addition, the polycrystalline PbX (X = S or Se) thin film grown on the amorphous thin film was verified by the X-ray diffraction (XRD) method that has a well known crystal structure cubic (cubic) structure. Although the thickness of the PbX (X = S or Se) thin film used for the analysis of RBS and XRD was very thin, it was confirmed that PbS having excellent crystallinity was grown by showing a clear XRD peak.

In view of the state of the precursor and the convenience of the process, in the PbX (X = S or Se) thin film growth method according to the present invention, in contrast to the coordination compounds mainly used in the manufacture of thin films such as PbS, PbO, etc. In the case of using a tetraalkyl lead precursor in the liquid state, it is possible to save material even more, and it is easy to charge the source material, which is advantageous in terms of production cost. In addition, since the metal organic substances are covalently bonded to the functional groups, the reactivity is much stabilized, so that the thickness uniformity of the thin film and the reproducibility of the process are excellent. In addition, the organometallic compounds used in the present invention have an advantage that does not contain oxygen that easily bonds with Pb.

In addition, the phosphor manufacturing method of the present invention for achieving the above object, in the phosphor manufacturing method consisting of a light emitting region containing the parent material region and the emission center ion is accelerated, the parent material growth reaction and the light emitting region growth Separating the reaction alternately and repeatedly performing a number of times to prepare a phosphor, using the organometallic compound Pb covalently bonded to the functional group as a Pb-precursor as described above Pb-precursor and H ₂ X (X = S Or by reacting and growing Se) so that PbX (X = S or Se) is added to the parent material. As a result, the phosphor manufacturing method of the present invention provides a phosphor having high brightness and high color purity.

In the phosphor manufacturing method of the present invention in which PbX (X = S or Se) is added to a mother material by atomic layer deposition using an organometallic compound as a Pb-precursor, the Pb ²⁺ ion, which is a light emitting center ion, is formed of Pb ²⁺ -. It is possible to grow PbX (X = S or Se) by adjusting it to exist in the form of dimer, whereby a range of concentrations of Pb ²⁺ from 0.2 to 4.0 mol.% (A considerably wider range) Irrespective of the concentration, a phosphor having a very high color purity and a very high luminance can be obtained.

That is, when deposition of II-VI compounds such as CaS, CaSe, SrS, SrSe, ZnS, ZnSe, BaS, BaSe, MgS, MgSe, etc., PbX (X = S or Se) is added according to the method of the present invention. The resulting product acts as a fluorescent layer. When PbX (X = S or Se) is selectively grown to emit light only by dimer, that is, the organometallic compound Pb-precursor is converted into a dimer intermediate. By forming and adsorbing on the growth surface in a dimer state, it is possible to produce a phosphor that can obtain a constant chromaticity in a wide concentration range. Preferably, the growth rate of the PbX is 0.005-0.6 Å / cycle.

In addition, as will be described in detail in the embodiments of the present invention to be described later, in order to form the PbX (X = S or Se) in the dimer state in the phosphor manufacturing method of the present invention, the atomic layer is performed at a temperature of 150 ~ 500 ^° C Forming by the deposition method, the thin film of the parent material region A Å, and the light emitting region thin film B Å alternately growing N times to grow a phosphor film having a thickness of [N × (A + B)] 되, It is preferable to form said B into 0.005-0.6 kPa. In addition, the parent material growth reaction is repeated a times and the light emitting region growth reaction is performed n times alternately, but b is preferably set to 2 or less at a growth temperature of 350 ^° C. or more.

In general, in the case of atomic layer deposition, it has been known that precursors should not decompose themselves by surface reaction at the reaction temperature. Therefore, in the growth of PbX (X = S or Se) using atomic layer deposition, Pb-precursor has decomposition temperature higher than reaction temperature and coordination compounds such as thd- and dedtc- Halogen compounds have been used. However, the present invention shows that the Pb is capable of growing a thin film having excellent growth reaction properties and thin film properties by using an organometallic compound precursor having a tetravalent covalent bond.

As an example, even in the case of tetraethyl lead, which boils in the air at 198 ° C. and partially decomposes at 100 ° C. or more, it is possible to grow a very uniform PbS thin film at a reaction temperature of 300 ° C. or more by atomic layer deposition. The reason is that the precursor in the form of lead IV is in a form of chemistry that favors the formation of PbS, which is a bonded state of lead II, by forming an intermediate that is favorable for some bonds to decompose or grow into dimers at the reaction temperature. This is because they form chemical species.

Meanwhile, in a conventional fluorescent layer manufacturing method, Pb ²⁺ ions added in a PbS or PbSe state in a group II-VI compound, that is, CaS, CaSe, SrS, SrSe, ZnS, ZnSe, BaS, BaSe, MgS, and MgSe parent materials. They have the same cubic-crystal structure as the parent material and also have a 2+ ion state like the group II ions of the parent material, so they are easily substituted into the parent material without the need for adding charge compensators. Thus, Pb ²⁺ ions easily form clusters or aggregates in which several are bound together in addition to the monomer state. These findings indicate that in PL studies such as CaS: Pb ²⁺ , CaSe: Pb ²⁺ , SrS: Pb ²⁺ , and SrSe: Pb ²⁺ , the excitation and emission spectra appear different for each study, with multiple peaks overlapping. And also proved experimentally that the spectra are not explained by any particular energy transition process (S. Asano, N. Yamashita, and Y. Nakao. Phys. Stat. Sol. (B) 89). , 663 (1978). In the ultraviolet region for monomer (monomer) - Pb ²⁺ by monitoring the change in the spectrum according to the amount of Pb ²⁺ by only adjusting the concentration to study the state of monomer (monomer) for Pb ^2+: As an example, CaS The emission spectrum was shown, and the wavelength was only 355, 364 nm for CaS: Pb and 371, 380 nm for CaSe: Pb. As the concentration increases, the PL peak shifts to longer wavelengths. However, it was not possible to produce materials by adjusting them to selectively emit light of any specific wavelength regardless of the concentration.

In the case of SrS: Pb ²⁺ , the monomer shows an emission spectrum at around 368 nm and for dimers at around 500 nm. According to the present invention, even in the case of SrS: Pb, electroluminescence can be obtained in which only a single peak near 500 nm appears.

In the CaS: Pb phosphor, which is an example, Pb ²⁺ ions have a radius of 1.20 μs and Ca ²⁺ ions have 0.99 μs, so that about 20% of lattice mismatch exists, and when Pb is included in a large amount, crystallinity deteriorates and Pb Regardless of clustering of ²⁺ ions, EL (electroluminescence) and CL (cathodoluminescence) properties are deteriorated. Therefore, in the present invention, Pb ²⁺ ions in a constant state exist regardless of the concentration within a concentration range in which excessive Pb is included and does not significantly reduce the crystallinity of the parent material, that is, light in a constant wavelength region in the EL process or the CL process. The resulting MX: Pb compound (M = Ca, Sr, Zn, Ba, Mg; X = S, Se) phosphor is provided, which greatly improves the luminance and chromaticity of the phosphor.

On the other hand, the phosphor prepared by the method of the present invention as described above can be applied to the electroluminescent device, thereby greatly improving the characteristics of the electroluminescent device. The structure of the electroluminescent device includes both a conventional structure and an inverted structure utilized in an active-matrix or the like. In addition, the phosphor of the present invention can be applied to PL (Photluminescen), cathode (CL) light emitting phosphor.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view of adding a layer containing light emitting center ions to a phosphor base material;

2 is a schematic diagram of an atomic layer deposition apparatus of a traveling wave reactor type as an example of a deposition method for applying the present invention.

3 is a spectrum showing EL peaks of CaS: Pb phosphors having different concentrations of Pb ²⁺ ions.

FIG. 4 is a spectrum showing the change in EL peaks as the thickness of the layer including the light emitting ion is increased in FIG. 1; FIG.

Fig. 5 is a spectrum showing the cathodoluminescence (CL) peak of a CaS: Pb phosphor having a Pb ²⁺ ion concentration of 0.7at.% Compared with a conventional well-known Zn: Ag phosphor. (A) and the inverted structure (b) grown on an opaque substrate, respectively, when the structure of the type thin film EL device (AC-TFELD) is grown on a transparent substrate.

7 is a luminance curve of a CaS: Pb blue electroluminescent device prepared by atomic layer deposition using the method presented in the present invention.

8 (a) and 8 (b) are electroluminescence spectrum characteristics diagrams of CaS: Pb blue electroluminescent devices prepared using Pb (thd) ₂ and tetra-ethyl lead as Pb precursors.

* Explanation of symbols for main parts of the drawings

1-5: valve 6: transparent substrate

7 transparent electrode 8 lower insulating layer

9: phosphor thin film 10: upper insulating layer

11 metal electrode 12 opaque substrate

13: refractory metal electrode

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings so that those skilled in the art may easily implement the technical idea of the present invention. do.

Pb ²⁺ ions have a 6s ² electron array in the outermost electron energy level of the ground state, and when energy is received, they transition to the 6s ¹ 6p ¹ state and return to the ground state to emit light. Due to the nature of these energy levels, the state of ions and the surrounding parent material are greatly affected.

This embodiment relates to a CaS: Pb blue phosphor having a high color and a very high luminance because the PS ²⁺ ions are selectively present only in a dimer state suitable for emitting blue color in CaS or CaSe, and a method of manufacturing the same. For reference, general blue phosphors are known to decrease luminance as the color is closer to pure blue. In addition, Ag is doped in SrS: Cu and Ag blue phosphors grown by magnetron sputtering, and the color shifts to pure blue. The brightness tended to decrease somewhat.

As a phosphor manufacturing method, an MX: Pb compound in which a small amount of PbX (X = S or Se) is added to an MX (M = Ca, Sr, Ba, Zn, or Mg; X = S or Se) parent material is used to change the chemical state thereof. The process of finely controlled growth can be briefly described as follows. In the process of doping PbX in the MX base material, first, the MX compound is grown to a certain thickness, and then PbX is grown to a certain thickness so as to satisfy the desired concentration ratio. The ash growth thickness is determined by the concentration of the desired Pb ²⁺ ion and its growth rate. The basic concept of this growth method is called atomic layer deposition or atomic layer chemical vapor deposition.

As an embodiment of the present invention, a phosphor and a method for producing the same, in which most Pb ²⁺ ions exist in a dimer state by adding PbS to CaS, are introduced.

As shown in FIG. 1, if CaS is grown a certain thickness (a cycles) and then PbS is grown n times by a certain thickness (b cycles), the thickness (T) of the CaS: Pb compound fluorescent film is expressed by Equation 1 below. Can be represented as:

T = {(a × A) + (b × B)} × n

Where A and B are the growth rates of CaS and PbS, and c, the concentration of Pb ²⁺ ions, is represented by Equation 2 below.

c (mol.%) = (b x B) / {(a x A) + (b x B)}

As such, by controlling the cycle ratio, the concentration of Pb ²⁺ ions can be doped to a desired concentration. The concentration of Pb can be excellently maintained, unlike previous studies in which Pb is doped differently according to the concentration of Pb. In the range, it can selectively grow so that only light emission by a dimer is dominant.

As an example of an atomic layer deposition method for applying the present invention to FIG. 2, a schematic diagram of atomic layer deposition of a traveling wave reactor type is shown.

Atomic layer deposition is a deposition technique that utilizes surface chemical reactions on the substrate surface. As an example, the process of depositing PbS-added Group II-VI metal sulfides using M-precursors (M = Ca, Sr, Zn, Ba, or Mg) and H ₂ S, Pb-precursors is described below. .

In the case of chemical vapor deposition, all reactants may be injected and grown simultaneously at a desired composition ratio, or may be repeatedly performed by separating the growth of metal sulfide (MS) and the growth of lead sulfide (PbS). However, in the case of the atomic layer deposition method, the valves 1 to 5 shown in FIG. 2 are adjusted independently, so that two or more valves are not opened at the same time in the following order.

1) Open valve (1) and inject M-precursor vapor with carrier gas. This causes the M-precursor reactant to adsorb to the substrate surface.

2) Open valve (2) and inject nitrogen or inert gas. This removes all molecules that are not adsorbed to the surface of the M-precursor reactant.

3) Open the valve (3) and inject H ₂ S gas. As a result, the H ₂ S gas is surface-reacted with the M-precursor reactant adsorbed on the substrate to grow the MS thin film and generate volatile byproducts.

4) Open the valve (4) and inject nitrogen or inert gas. This removes excess H ₂ S molecules and the volatile reaction product between the M-precursor and H ₂ S.

5) The process of 1) -4) is repeated several times.

6) Open valve 5 and inject Pb precursor. As a result, the Pb precursor is adsorbed onto the metal sulfide (MS) surface.

7) Inject nitrogen or inert gas. As a result, all of the Pb precursor molecules that are not adsorbed on the surface are removed.

8) Inject H ₂ S. As a result, the H ₂ S reactant is surface-reacted with the Pb precursor molecules adsorbed on the substrate to grow the PbS thin film and generate volatile byproducts.

9) Inject nitrogen or inert gas. This removes excess H ₂ S molecules and volatile reaction products between Pb precursor molecules and H ₂ S.

As a result of this reaction process, in the case of atomic layer deposition, the thin film can be grown at a deposition rate of 'one monolayer / 1 cycle' or less and MS: Pb (M = Ca, Sr, Zn, Ba, Alternatively, the composition of the Mg) thin film can be finely adjusted by controlling the number of cycle repetitions. In the case of chemical vapor deposition, the composition of the growth thin film is controlled by controlling the relative concentration ratio of the precursors.

In the prior art (prior research), the color changes according to the concentration of Pb ²⁺ ions in the phosphor, which is a monomer when Pb ²⁺ is low in concentration, and dimers are gradually formed when the concentration increases. On the other hand, clusters are formed at a certain concentration and turn green, and, unlike clusters, which are reported to have low luminance, in the present invention, only clusters of Pb ²⁺ -dimers are present regardless of the concentration. Can be.

In order to grow to exist only in a dimer regardless of the concentration, a reaction precursor having certain characteristics is required. An example is tetraethyl lead, which is present as tetraethyl lead at room temperature but begins to decompose at temperatures above 100 ^o C and in a reactor maintained at a reaction temperature above 200 ^o C. It is easily decomposed, and it is more likely to form Pb ₂ (C ₂ H ₅ ) ₆ (hexaethyl dilead), and Pb-Pb bonds are stronger than Pb-C bonds, so they form a dimer at the reaction site on the surface. Will be adsorbed. The production of Pb ₂ (C ₂ H ₅ ) ₆ is usually supported by synthetic reactions with tetraethyl lead. Given the tendency of Pb to agglomerate with each other, if the growth rate is maintained at a low growth rate that is not adsorbed to the nearest neighbor site, i.e., if the growth rate is 0.2 monolayer or less, then the desired As such, it is possible to dope the Pb existing only in the dimer form. The limit of growth rate of 0.2 monolayer is lower if the migration tendency of Pb is large.

In addition, Pb ²⁺ ions introduced into the dimer by clustering or aggregating PbX (X = S, Se) growth reactions are inserted several times and dozens of times. By not forming aggregates, it is possible to grow phosphors which selectively generate only light by dimers. This effect is noticeable above a certain temperature depending on the temperature variation of the growth equipment and the type of reaction precursor.

Precursors with similar reaction properties to the tetraethyl lead used in the examples were combined with methyl, ethyl, propyl, isopropyl, cyclohexyl groups, and the like. Tetraalkyl lead, and tetraaryl lead precursors (tetraphenyl lead, tetracyclohexyl lead, triphenylbenzyl lead, diphenyldicyclohexyl lead, etc.) bound to phenyl, benzyl groups, etc. Precursors exhibiting similar reaction properties can be used for the same purpose.

As an example, the Pb ²⁺ ions show that only a dimer is present in almost all of the specific conditions and thus only shows generation of light by the dimer. An embodiment of the present invention is a case of a CaS: Pb electroluminescent device which shows high purity blue regardless of the concentration, that is, even at a concentration of 0.6-4.0 mol.%.

Ca (thd) ₂ (thd = 2,2,6,6-tetramethyl-3,5-heptandionate) and H ₂ S were used to grow CaS, and also tetraethyl lead and H ₂ S In the process of growing PbS by reaction, the total concentration of Pb ²⁺ is 0.01 Å / cycle when the growth rate of PbS is 320 ^o C, about 0.15 Å / cycle when 400 ^o C and the growth rate of CaS is 0.35-0.45 Å It can be determined by adjusting the repetition ratio in consideration of / cycle. Since the growth rate of PbS is 0.15 mA / cycle or less at a temperature of 400 ^° C. or less, the surface coverage per cycle is 0.1 or less. That is, less than one in ten possible reaction sites will bind PbS. Therefore, by controlling the number of times, formation of an aggregate can be greatly suppressed. A schematic cross-sectional view of the MX: Pb thin film grown in this manner is shown in FIG. 1.

Of CaS and PbS growth cycle (cycle) by growth by controlling the a and b, regardless of the concentration of Pb ²⁺ ions Pb ²⁺ ion is present as a dimer (dimer) CaS showing a certain wavelength and a chromaticity: Pb phosphor thin film The characteristics of are shown in Table 1 below and FIG. Table 1 shows the phosphor thin film prepared by increasing the concentration of Pb ²⁺ ions by fixing the thickness of one cycle of growth of PbS at 400 ^° C., ie, the thickness of PbX in FIG. 1, and reducing the number of cycles of CaS. Show chromaticity. When the PbS concentration was about 0.6 mol% and the PbS concentration was increased to about 2.5 mol% or more, the color coordinates were almost the same and only the luminance was changed.

Experimental results of controlling the concentration of Pb ²⁺ ions by maintaining the constant growth thickness of PbS and controlling the number of CaS growth cycles Pb concentration (mol.%) CIE color coordinates x y 0.6 0.15 0.11 0.8 0.14 0.10 1.0 0.15 0.11 1.4 0.15 0.10 2.0 0.15 0.11 2.5 0.14 0.12

FIG. 3 shows EL spectra when the concentrations of Pb ²⁺ ions are 0.6 mol.%, 0.8 mol.%, And 1.4 mol.%, And the wavelengths are almost the same even when Pb ²⁺ is included. In particular, unlike the previous studies in which EL lines with wide line widths and different positions of EL spectra overlap each other, they appear as single peaks with narrow line widths.

The results shown in Table 1 and Figure 3, unlike the previous studies that confirmed the blue EL only in a narrow range of 1-1.5 mol.% In the present invention optionally includes a dimer irrespective of the concentration of Pb ²⁺ ion It means that the fluorescent material is made. However, when the Pb concentration becomes higher than 4.0 mol.%, The crystallinity of the parent material deteriorates and the luminance is greatly reduced.

On the other hand, the results of Figure 4 is to observe the characteristics of the fluorescent film was produced while the number of growth cycles of CaS is constant and the thickness of growth of PbS is changed once. In other words, the effect was examined by controlling the growth cycle number b of PbS. In FIG. 3, in the CaS: Pb phosphor grown at a growth temperature of 350 ^° C., (b) shows the EL spectrum when the PbS growth thickness is adjusted to 2 times as in (a) and (c) as 3 times as in (a). Compare with each other. As shown in FIG. 4, it can be seen that as the one-time PbS growth thickness increases, the peak position of the EL spectrum shifts to a longer wavelength and the width of the peak increases. This result is also well represented in CIE color coordinates. Table 2 below shows the change in concentration and the change in CIE color coordinates according to the change in the number of growth cycles b of PbS. Increasing the y value in the CIE color coordinates indirectly shows that the peak shifts to longer wavelengths. x is the red inclusion ratio, y is the green inclusion ratio, and z (z = 1-xy) corresponds to the blue inclusion ratio. Therefore, smaller x and y values mean better blue purity. As shown in Table 2 below, the chromaticity of light emitted from the CaS: Pb phosphor is significantly affected by the single growth thickness of PbS. Even when the Pb concentration is less than 0.1 mol.%, Once the growth thickness of PbS is adjusted, light in the green region is generated.

The results of FIGS. 3 and 4, Tables 1 and 2 above show that the color coordinates of the CaS: Pb phosphors are not simply determined by the concentration of Pb, but are determined by the state of Pb ²⁺ ions. As the size of the semiconductor particles decreases, the band gap increases, and it can be seen that the band gap is well matched with the "quantum dot effect" that can control the band gap according to the particle size.

These results show that the present invention actually produces MX: Pb ²⁺ (M = Ca, Sr, Ba, Zn, Mg; X = S, Se) compounds containing a certain type of Pb ²⁺ ion regardless of the total concentration of Pb. Show that you can. As an example, CaS: Pb blue EL phosphors that emit light of a specific wavelength regardless of concentration could be prepared by appropriately adjusting the single growth thickness of PbS, that is, the number of cycles, at a growth temperature of 350-400 ^° C., respectively.

The above-mentioned phosphor manufacturing method is available in CL phosphor production as mentioned above. As an example, FIG. 5 is a result showing CL characteristics of a CaS: Pb (Pb concentration: 0.7 atom.%) Fluorescent film having a thickness of 500 kV prepared using tetraethyl lead. The peak wavelength of the CL peak is 435-440 nm, which is more than seven times stronger than the commercially available CRT phosphor, ZnS: Ag powder. On the other hand, Pb ²⁺ ions have a 6s ² outermost electronic structure, so the MX parent material The state of a lot is affected. Therefore, since the crystal state of the parent material changes depending on the growth temperature, some wavelength shift is accompanied. However, the degree is not so large compared to the change in the thickness of single growth of PbS.

The above results are contrary to the tendency of gradually changing color from UV to blue and green as the concentration of Pb increases in the prior art (prior art).

As a prior patent regarding the thickness of a light emitting region including a light emitting center ion, a prior patent in which a ZnS: Tb green EL fluorescent layer is grown by atomic layer deposition (US Patent 5314759) has a thicker Tb ₂ S ₃ light emitting layer, that is, It has been argued that the larger the one-time growth thickness of the mentioned Tb ₂ S ₃ layer is, the more advantageous it is for obtaining high brightness. However, in the present invention, as shown in Table 2, in the case of Pb ²⁺ ions, since the chromaticity is deteriorated by clustering, the smaller the growth thickness is, the more favorable it is to obtain blue color.

Phosphor material selectively generated only by light emission by Pb ²⁺ dimer shown in the present invention can not be manufactured by physical vapor deposition such as a method of heat-treating conventional mixed powder, sputter deposition, electron beam deposition Material. Fluorescent materials which selectively include predominantly dimers, which are preferred embodiments of the present invention, and generate only blue color with little desirable ultraviolet emission, are in units of less than one monilayer, i.e., growth rate is 0.02-. It shows excellent characteristics when it can be adjusted to the level of 0.2 monolayer / cycle or less as about 0.6 Å / cycle.

In addition, as described above, the control of PbX single growth thickness is very important. Increasing the thickness of one-time growth increases the growth rate of PbX, which means that the Pb precursor adhesion coefficient is higher on PbX than on CaX, and XRD (X-ray diffraction) of PbX thin film under the growth temperature above 350 ^o C In the data, metallic Pb peaks begin to be observed and the amount of metallic Pb increases as the growth temperature increases. However, no metallic lead peaks were observed at above 420 ^° C under conditions in which the PbX single growth thickness in the parent material was adjusted as small as possible. This explains well that it is very important to adjust the thickness of PbX one-time growth in accordance with the temperature in the present invention.

The growth rate depends on the type of precursor used in the growth reaction system, which is one of the important variables. For example, using Pb (thd) ₂ as the precursor of Pb for CaS: Pb phosphor growth, the growth rate is 10 times faster than that of tetra-ethyl lead in the 300-350 ^o C range. In this case, the blue EL phosphor having excellent chromaticity could not be grown, and the luminance was also very low.

As another example of controlling the color of light emitted by using a growth rate, SrS: Pb emits ultraviolet light when Pb is present as a monomer, and generates cyan light when present as a dimer. . Therefore, the above experimental results indicate that the selective formation of dimer Pb ²⁺ ions during SrS: Pb growth can selectively grow a cyan phosphor near wavelength 500 nm. The present invention is contrary to the result of generating light close to white in a very wide wavelength range as the concentration increases in the previous study.

Phosphors prepared in this manner are used as high purity and high luminance phosphors in electroluminescent devices and cathode light emitting devices.

6A and 6B, the structure of the AC-TFELD, which is a main application device of the present invention, is grown on a transparent substrate (FIG. 6A) and an inverted structure grown on an opaque substrate (FIG. 6B). It is shown.

The structure of FIG. 6A is a structure of an electroluminescent device of a general type, and the structure of FIG. 6B is a representative structure of an active-driven thin film EL device.

Referring to FIG. 6A, the AC-TFELD has a double insulation structure, for example, indium tin oxide (ITO) or ZnO on a transparent substrate 6 such as glass or borosilicate glass. The transparent electrode 7 is formed as a transparent conductive thin film such as aluminum-doped zinc oxide (Al), and a lower insulating layer 8 is formed on the transparent electrode 7, and the lower insulating layer 8 is formed. On top of the phosphor thin film 9 containing Pb ²⁺ light emitting center ions added by the method according to the present invention is formed, the upper insulating layer 10 is formed on the phosphor film thin film 9, A metal electrode 11 such as Al, Au, W or the like is formed on the upper insulating layer 10. That is, the upper and lower insulating layers 8 and 10 surround the phosphor thin film 9. The insulating layers 8 and 10 allow high electric field to be applied to the phosphor thin film 9, and serve to protect the phosphor thin film 9 from the external environment.

In addition, referring to FIG. 6B, an inverted active-driven thin film EL device includes a refractory metal 13 such as W or Mo, for example, on an opaque substrate 12 such as silicon (Si) or alumina (Alumina). And a thin film of phosphor containing Pb ²⁺ luminescent center ions formed by the method according to the present invention, the first insulating layer (8) being formed on the metal electrode (13). (9) is formed. The second insulating film 10 is formed on the phosphor thin film 9, and the transparent electrode 7 is formed on the second insulating film 10. The light emitted from the phosphor thin film 9 is emitted through the transparent electrode 7.

As described above, the method of forming the phosphor thin film 9 may use both the atomic layer deposition method and the chemical vapor deposition method using the apparatus as shown in FIG. 2, which is a metal organic compound precursor of Pb and H _2. It utilizes the growth method of PbX thin film using reaction with X (X = S, Se).

The present invention proposes a method of manufacturing a high luminance blue fluorescent layer required for realizing natural colors in the field of AC-driven thin film electroluminescent device technology, and also uses the method to provide a blue active-driven thin film electroluminescent device. It can manufacture. In addition, the phosphor thin film 9 may be implemented as one of three primary color fluorescent films to provide a color electroluminescent device, and the phosphor film may emit white color by a filter.

PbS thin film, which is the main result of the present invention, is a material that is usefully used as a solar cell, an infrared detector, etc. in addition to an electroluminescent device.

In the electroluminescent device structure of the present embodiment, a fluorescent layer having a structure in which two or more kinds of thin films of CaS, SrS, ZnS, BaS, and MgS has a multilayer structure as a parent material of the phosphor thin film 9 may be used. Since CaS, SrS, ZnS, BaS, and MgS polycrystalline thin films all have cubic structures, ZnS, which is particularly excellent in crystallinity, improves crystallinity of neighboring thin films and restricts excessive flow of charge. PbS may be added only in one type of parent material or in some parent materials, or may be added uniformly in all the parent material thin films.

In the present invention, a PbX (X = S, Se) thin film is formed of an organometallic compound precursor and H ₂ X by using one of the traveling wave reactor type atomic layer deposition method, the atomic layer deposition method using a compound beam, and the chemical vapor deposition method shown in FIG. It is characterized in that the deposition through the reaction of, and by using this to grow the above-mentioned phosphor by atomic layer deposition or chemical vapor deposition. And it is characterized in that applied to the electroluminescent device and cathode light emitting device.

As such, the present invention proposes a method of growing a PbX thin film by reacting with H ₂ X by atomic layer deposition and chemical vapor deposition using Pb-precursors with tetravalent covalent bonds. In addition, II-VI compound semiconductor growth processes such as CaS, CaSe, SrS, SrSe, ZnS, ZnSe, BaS, BaSe, MgS, and MgSe are added to IV-VI compound growth processes, such as PbX, at regular intervals. The layer can be grown. In particular, a phosphor in which a Pb ²⁺ ion, which is a light emitting center ion, is selectively present in a dimer state within a certain range of conditions may be manufactured.

On the other hand, although not described as a specific embodiment of the present invention, in the method of manufacturing an electroluminescent device, it can have a variety of applications and modifications as follows.

The fluorescent layer is an atomic layer deposition process of a polycrystalline thin film, or a multilayer thin film thereof, using any one of CaS, SrS, ZnS, BaS, MgS, CaSe, SrSe, ZnSe, BaSe, and MgSe added Pb. Tetra-alkyl lead (IV) (alkyl = methyl, ethyl, propyl, isopropyl, cyclohexyl), tetraaryl lead (IV), alkylaryl lead, dicyclo Dicyclopentadienyl lead (II) or bistrialkylsilyl lead and the like can be used.

In addition, it may be composed of a phosphor composed of one or more thin films, the multilayer structure is a structure in which the ZnS layer and the CaS: Pb layer is repeatedly grown one or more times, SrS: Pb layer and CaS: Pb layer once It may have a structure that is repeatedly grown above, a structure in which the ZnS layer, the SrS: Pb layer and the CaS: Pb layer are repeatedly grown one or more times. In addition, a lead (IV) -organic metal compound (MO) or lead (II) -organic metal compound (MO) precursor may be used in a multilayer structure.

In addition, the fluorescent layer has a multilayer structure of at least one layer, and at least one layer of CaX (with PbX (X = S, Se) added 0.2-4.0 mol% (amount of Pb corresponds to 0.1-2.0 at.%)) X = S, Se) polycrystalline thin film, at least one layer of PbX (X = S, Se) 0.2-4.0 mol% (Pb amount is 0.1-2.0 at.%) Added SrX ( X = S, Se) It may also be composed of a polycrystalline thin film.

As an example, an electroluminescent device manufactured by using a tetraethyl lead precursor in CaS having a relative amount of PbS of about 0.2 to 4.0 mol.% In a fluorescent layer grown in CaS has a chromaticity (x, y). Pure blue light of x = 0.12-0.19 and y = 0.07-0.20 was generated. In particular, when selectively prepared for the generation of light in Pb ²⁺ ion-dimers, the chromaticity is within the narrow range of (0.14, 0.07)-(0.15, 0.15), with a pure EL peak showing a peak between 440-450 nm. Blue phosphors could be prepared. The luminance showed a value of 100 cd / m ² or more at 60 Hz. This result shows the brightness several times tens or more times the result prepared using the existing coordination compound.

FIG. 7 shows a luminance curve of a CaS: Pb blue electroluminescent device manufactured by using atomic layer deposition at 400 ^° C. FIG. Under these manufacturing conditions, the luminance was 85 cd / m ² at the driving voltage 25V higher than the threshold voltage, and the maximum luminance was much larger. At this time, the chromaticity was (0.15, 0.10) which was pure blue. This brightness is more than 30 times better than that of Finland's E. Nykanen.

The EL spectrum of the CaS: Pb electroluminescent device fabricated based on the present invention was compared with the results prepared using thd-compounds of Pb. These devices have the same growth conditions as the same growth equipment and only differ in precursors. 8A and 8B show electroluminescent spectral characteristics of electroluminescent devices prepared using thd-compound and tetraethyl lead, respectively. As shown in FIG. 8B, the wavelength of the EL peak maximum of the electroluminescent device grown using tetraethyl lead is 440-445 nm and the full width at half maximum is narrower than 60 nm. However, the spectrum of devices fabricated using Pb (thd) ₂ is very broad and long wavelength.

Although the technical idea of the present invention has been described in detail according to the above preferred embodiment, it should be noted that the above-described embodiment is for the purpose of description and not of limitation. In addition, those skilled in the art will understand that various embodiments are possible within the scope of the technical idea of the present invention.

As described in detail above, when the metal organic precursor according to the present invention is used, the thin film uniformity is superior to that of the coordination compound, and even in the case of the precursor of +4 bound state, +2 is changed to the bound state during the reaction. Phosphorus PbS is effective to grow.

Particularly in the case of atomic layer deposition, in which the precursor must behave at a stable temperature at the reaction temperature, even in the case of tetraethyl lead, which has a boiling point of 198 ° C in the air and partially decomposes at 100 ° C or higher, the reaction temperature is very uniform even at a reaction temperature of 300 ^° C or higher. There is an effect that can grow a PbS thin film.

In addition, the present invention can deposit a PbS thin film by the reaction of the organometallic compound precursor and H ₂ S by using one of the following techniques: traveling wave reactor type atomic layer deposition, atomic beam deposition using a compound beam, chemical vapor deposition, It is effective to select a variety of manufacturing methods, and also by using this as a growth method of the fluorescent layer can be produced excellent blue electroluminescent device and cathode light emitting device, especially when applied to the electroluminescent device and cathode ray-emitting device. It has an effect.

In addition, in the present invention, the fluorescent film to which PbX is added to the MX (M = Ca, Sr, Zn, Ba or Mg; X = S or Se) parent material is selectively adjusted so that PbX ⁺ ion is present in the dimer state. By presenting a method for producing a phosphor having a very high color purity and a very high brightness under the conditions of the concentration of 0.2-4.0 mol.% Of Pb ²⁺ . According to the present invention, when a phosphor containing Pb ²⁺ ions as a light emitting ion, a reaction system having a Pb ²⁺ addition rate of 0.02-0.6 Å / cycle in the parent material is selected, and the Pb ²⁺ ions are dimers. By using a reaction precursor that participates in the reaction in a state, it is possible to produce a high-luminance phosphor that emits light having a very high color purity.

As a result obtained in the embodiment of the present invention, the best color coordinate of CaS: Pb, which is a blue phosphor selectively generating only light by Pb ²⁺ dimer, is (0.14, 0.07), which is the most ideal of the blue color of the cathode ray tube. The same value was obtained, and the brightness was higher than 100 cd / m ² at the AC-60Hz driving condition when applied to the electroluminescent device. This value corresponds to a multiple of the best blue phosphor of the presently disclosed electroluminescent device, which is much superior to previous studies in which the luminance is greatly reduced by clustering when the concentration is increased.

In addition, the present invention can obtain very excellent properties in terms of reproducibility and uniformity of the process, and in particular, in the case of liquid precursors such as tetraalkyl lead (IV), the process cost in terms of material, time, and attraction is much reduced. have.

Claims (43)

A parent material growth reaction and Pb ²⁺ ions to form a parent material containing a group II element (M = Ca, Sr, Zn, Ba or Mg) and a group VI element (X = S or Se) are incorporated into the parent material. In the manufacturing method of the fluorescent film which adds Pb ²⁺ ion as a light emitting center ion in the said parent material grown using the light emitting center ion addition reaction for adding as a light emitting center ion, The luminescent ions addition reaction is performed by using any one of tetraalkyl lead, tetraaryl lead, alkylaryl lead, dicyclodipentadienyl lead, or bistrialkylsilyl lead as a Pb-precursor and the Pb-precursor and H ₂ X ( And X = S or Se) reacts to form PbX. The method of claim 1, The alkyl group or aryl group of the tetraalkyl lead, tetraaryl lead, alkylaryl lead and bistrialkylsilyl lead is at least one of a methyl group, ethyl group, propyl group, isopropyl group, cyclohexyl group, phenyl group or benzyl group Method of Making Membranes. The method of claim 1, The tetraalkyl lead is tetraethyl lead. The method of claim 1, The parent material is a II-VI compound formed by reacting M-precursor with H ₂ X (X = S or Se). The method of claim 1, The concentration of Pb ²⁺ ions in the fluorescent film is 0.2 ~ 4.0 mo1% method for producing a fluorescent film. The method of claim 1, The growth of the base material and the addition of the emission center ion proceed simultaneously, and the concentration of the Pb ²⁺ ions is controlled by the relative ratio between the concentration of the M-precursor and the concentration of the Pb-precursor. Way. The method of claim 1, And the parent material growth reaction and the emission center ion addition reaction are alternately performed. The method of claim 7, wherein After growing a thin film of the parent material region using the parent material growth reaction, a process of growing a PbX (X = S or Se) thin film using the light emitting ion addition reaction is repeated a plurality of times to grow a phosphor thin film of a desired thickness. The manufacturing method of the fluorescent film characterized by the above-mentioned. The method of claim 7, wherein The concentration of the Pb ²⁺ ions is controlled by the relative ratio between the thickness of the thin film of the parent material region and the thickness of the PbX thin film. The method of claim 7, wherein Method for manufacturing a fluorescent film, characterized in that the one-time growth thickness of the PbX thin film is 0.005 ~ 0.6Å. The method of claim 8, After the a growth reaction of the base material is carried out a (a is a natural number) cycle, the process of performing the light emitting ion addition reaction b (b is a natural number) cycle is alternately repeated a plurality of times to form a thin film and a PbX thin film of the base material region A method for producing a fluorescent film, characterized by growing. The method of claim 11, When the reaction temperature is 350 ℃ or more, the number of cycles b of the emission center ion addition reaction is 2 or less, characterized in that the manufacturing method of the fluorescent film. The method of claim 11, The growth rate of the PbX thin film is a manufacturing method of the fluorescent film, characterized in that 0.005 ~ 0.6 Å / cycle. The method of claim 1, The parent material growth reaction and the emission center ion addition reaction is a manufacturing method of the fluorescent film, characterized in that the reaction temperature is carried out in the range of 150 ~ 500 ℃. In a fluorescent film in which Pb ²⁺ ions are added as emission center ions in a parent material containing a Group II element (M = Ca, Sr, Zn, Ba or Mg) and a Group VI element (X = S or Se), The Pb ²⁺ ion is selected from tetraalkyl lead, tetraaryl lead, alkylaryl lead, dicyclodipentadienyl lead, or bistrialkylsilyl lead as the Pb-precursor and the Pb-precursor and H ₂ X (X = S or Se) is added to the base material in the PbX state formed by the reaction. The method of claim 15, The alkyl group or aryl group of the tetraalkyl lead, tetraaryl lead, alkylaryl lead, bistrialkylsilyl lead is at least one of a methyl group, ethyl group, propyl group, isopropyl group, cyclohexyl group, phenyl group or benzyl group Fluorescent film. The method of claim 15, The tetraalkyl lead is tetraethyl lead. The method of claim 15, The parent material is a fluorescent film, characterized in that the group II-VI compound formed by the reaction of the M- precursor and H ₂ X (X = S or Se). The method of claim 15, The concentration of Pb ²⁺ ions in the fluorescent film is characterized in that the fluorescent film 0.2 ~ 4.0 mol%. The method of claim 15, The phosphor film is a phosphor film formed by alternately stacking the parent material thin film and the PbX thin film containing the light emitting center ion a plurality of times. The method of claim 20, The thickness of one layer of the PbX thin film is 0.005 ~ 0.6 Å. The method of claim 21, The growth rate of the PbX thin film is a fluorescent film, characterized in that 0.005 ~ 0.6 Å / cycle. At least one parent material layer formed of a parent material comprising a Group II element (M = Ca, Sr, Zn, Ba, or Mg) and a Group VI element (X = S or Se), wherein all of the parent material layers Or in a multilayered fluorescent film in which part of Pb ²⁺ ions is added as a light emitting center ion, The Pb ²⁺ ion is selected from tetraalkyl lead, tetraaryl lead, alkylaryl lead, dicyclodipentadienyl lead, or bistrialkylsilyl lead as the Pb-precursor and the Pb-precursor and H ₂ X ( A fluorescent film having a multilayer structure, which is added to the mother material layer in a PbX state formed by reaction of X = S or Se). The method of claim 23, wherein The alkyl group or aryl group of the tetraalkyl lead, tetraaryl lead, alkylaryl lead, bistrialkylsilyl lead is at least one of a methyl group, ethyl group, propyl group, isopropyl group, cyclohexyl group, phenyl group or benzyl group A fluorescent film of a multilayer structure. The method of claim 23, The tetraalkyl lead is a tetraethyl fluorescence film, characterized in that tetraethyl lead. The method of claim 23, wherein The parent material is a multi-layered fluorescent film, characterized in that the group II-VI compound formed by reacting the M- precursor and H ₂ X (X = S or Se). The method of claim 23, wherein The parent material is a multi-layer fluorescent film, characterized in that formed of ZnX, CaX or SrX. The method of claim 23, wherein The concentration of Pb ²⁺ ions in the fluorescent film is a fluorescent film of a multilayer structure, characterized in that 0.2 to 4.0 mol%. The method of claim 23, wherein The fluorescent film is a fluorescent film having a multi-layer structure, characterized in that the fluorescent material thin film formed by alternately stacking the parent material thin film and the PbX thin film containing the light emitting center ion. The method of claim 29, The thickness of one layer of the PbX thin film is a multilayer film, characterized in that 0.005 ~ 0.6 Å. The method of claim 30, The growth rate of the PbX thin film is a multi-layer fluorescent film, characterized in that 0.005 ~ 0.6 ~ / cycle. An electroluminescent device comprising a fluorescent film prepared by the method of claim 1. An electroluminescent device comprising the fluorescent film of claim 15. An electroluminescent device comprising the fluorescent film of claim 23 having a multilayer structure. The method of any one of claims 32 to 34, wherein The electroluminescent device is an electroluminescent device, characterized in that the insulating film is provided on the upper and lower portions of the fluorescent film. Cathode light emitting device comprising a fluorescent film prepared by the method of claim 1. A cathode light emitting device comprising the fluorescent film of claim 15. In the PbX thin film manufacturing method, The Pb-precursor and H ₂ X (X = S or Se) are formed by using any one of tetraalkyl lead, tetraaryl lead, alkylaryl lead, dicyclodipentathienyl lead, or bistrialkylsilyl lead as the Pb-precursor. PbX thin film manufacturing method characterized in that the reaction to form a PbX thin film. The method of claim 38, The alkyl group or aryl group of the tetraalkyl lead, tetraaryl lead, alkylaryl lead and bistrialkylsilyl lead is at least one of a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclohexyl group, a phenyl group or a benzyl group Thin film manufacturing method. The method of claim 38, The tetraalkyl lead is tetraethyl lead, characterized in that the PbX thin film manufacturing method. The method of claim 38, PbX thin film manufacturing method characterized in that the reaction is made at 100 ~ 450 ℃. The method of claim 38, The growth rate of the PbX thin film is a PbX thin film manufacturing method, characterized in that 0.005 ~ 0.6 Å / cycle. 43. A PbX thin film prepared by the method of any one of claims 38-42.