JP4946576B2 - Light emitting element - Google Patents

Description

  The present invention relates to a light emitting element.

  Conventionally, a large area light source such as a backlight for a liquid crystal TV or a general illumination uses a cold cathode tube or a fluorescent lamp which is excellent in luminous efficiency and life. In recent years, there has been a demand for new light-emitting elements that can replace them.

  A light emitting diode (LED) is well known as a typical light emitting element. Conventionally, a compound semiconductor lattice-matched to a substrate such as GaAs or AlGaAs is formed on a single crystal substrate such as GaAs or InP using a liquid phase epitaxy method, a metal organic vapor phase epitaxy method, a vapor phase epitaxy method, or a molecular beam epitaxy. It was manufactured by epitaxial growth using a crystal growth method such as a taxi method and processing. However, since such LEDs use single-crystal substrates such as GaAs and InP that are more expensive than Si and glass, and do not exist in large areas, they can be used as point light sources for small areas such as lighting. The practical use is limited.

  On the other hand, there are known a dispersion type EL (electroluminescence) and a thin film type EL in which phosphor particles are sandwiched between electrodes and used as a light emitting element (see, for example, Patent Documents 1 and 2). Since such a light-emitting element can be easily manufactured using an inexpensive substrate, there is a great expectation for practical use.

Japanese Patent Laid-Open No. 8-183954 JP 2005-281380 A

  However, even the light-emitting elements described above are not yet sufficient to achieve the high level of light-emitting efficiency and life required for liquid crystal TV backlights.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a light-emitting element having excellent luminous efficiency and a long lifetime.

A light-emitting element of the present invention that solves the above problems includes a substrate, a light-emitting layer formed on the main surface of the substrate, and a pair of electrodes provided on the surface of the light-emitting layer opposite to the surface in contact with the substrate. A semiconductor polycrystal including an impurity element that forms a donor level and an impurity element that forms an acceptor level, and is present at a crystal grain boundary of the semiconductor polycrystal, includes a compound of different composition, a semiconductor polycrystalline ZnS crystal grains, the compounds of the composition different from the semiconductor polycrystals, _Cu 2 _S, are those wherein CuGaS 2, CuAlS ₂ or CuInS _2. According to the light emitting device of the present invention, by having the above configuration, high light emission efficiency can be achieved and sufficient light emission luminance can be maintained over a long period of time. Therefore, according to the present invention, it is possible to realize a light-emitting element having excellent luminous efficiency and a long lifetime.

  Note that the above-described effect of the present invention is obtained by applying the principle of DA pair emission in which electrons and holes are recombined through donor levels and acceptor levels formed in a semiconductor polycrystal. On the other hand, in an experiment that attempted to improve the light emission efficiency by increasing the concentration of the impurity element present at the grain boundary of the semiconductor polycrystal, a pair of electrodes were provided on one side of the light emitting layer to provide a space between the electrodes. This is based on the knowledge of the present inventors that the short circuit can be prevented very effectively. In addition, when the pair of electrodes are provided so as to sandwich the light emitting layer, it has been found by the inventors that it is impossible to achieve both improvement in light emission efficiency and long life. The reason for this is presumed as follows. In other words, in the light emitting layer containing semiconductor polycrystal, it is considered that the luminous efficiency is effectively improved when the impurity element is distributed in the thickness direction of the light emitting layer. Therefore, in a system in which an electric field is applied in the film thickness direction of the light emitting layer, it is difficult to suppress a current path due to the movement of impurity element ions from being connected between the electrodes. It is thought that.

Moreover, in the light emitting element of this invention, it is preferable that the compound which can form the said ZnS crystal grain and PN junction is the said sulfur compound containing a copper atom. That is, the light emitting layer, a ZnS crystal grains present in the grain boundaries of the ZnS crystal grains, is preferably those containing the above-described sulfur compound containing copper atom. According to such a light emitting element, both the light emission efficiency and the long life can be achieved more reliably at a higher level.

  Note that the above-described effects of the light-emitting element are as follows. (1) The light emission in the light-emitting layer in which a sulfur compound containing a copper atom is present in the crystal grain boundary of the ZnS crystal is the donor level formed in the ZnS crystal. It is considered to be due to DA pair emission in which electrons and holes are recombined through the acceptor level, and stable and highly efficient emission can be obtained even when the defect density is high. (2) Crystal It is considered that a sulfur compound containing a copper atom present at a grain boundary and ZnS as a crystal form a pseudo PN junction, and the probability that electrons and holes are recombined in ZnS increases, and (3) light emission Since an electric field is applied to the layer in a direction parallel to the substrate, a short circuit due to movement of copper ions at the grain boundary is less likely to occur than when an electric field is applied in the film thickness direction of the light emitting layer. The effects (1) and (2) are obtained effectively. Is possible, is achieved what was the present inventors for reasons to infer.

In the light emitting device of the present invention, it is preferable that the Cu ₂ S, CuGaS ₂ , CuAlS _2, or CuInS ₂ exist in a direction from the surface opposite to the surface contacting the substrate of the light emitting layer toward the substrate .

  In this case, it is possible to further increase the concentration of the sulfur compound containing copper atoms in the light emitting layer while preventing the short circuit, and it becomes easier to obtain high light emission efficiency.

In the light-emitting device of the present invention, when the light-emitting layer contains ZnS crystal grains and a sulfur compound containing a copper atom present at the crystal grain boundary of the ZnS crystal grains, the X-ray diffraction pattern of the light-emitting layer When the X-ray diffraction peak intensity attributed to the (111) crystal plane is I ₍₁₁₁₎ and the X-ray diffraction peak intensity attributed to the (110) crystal plane is I ₍₁₁₀₎ , the peak intensity ratio (I _{(111) )} / I ₍₁₁₀₎ ) is preferably 80 or more.

  In this case, a light-emitting element having a long lifetime and high light emission efficiency can be realized more easily. This is because a ZnS crystal having a columnar structure having an appropriate grain size is included in the light emitting layer at a high abundance ratio, so that a sulfur compound containing a copper atom existing in a crystal grain boundary becomes a columnar shape with a high probability, and more effectively. This is considered to contribute to light emission and to further reduce the current path formed by the sulfur compounds.

  Moreover, in the light emitting element of this invention, it is preferable that the copper concentration in the said light emitting layer is 0.1 atomic%-5 atomic%. In this case, a light-emitting element that emits light stably for a long period of time with a practically sufficient luminance can be more reliably realized.

Moreover, in the light emitting element of this invention, it is preferable that the said light emitting layer contains 1 or more types of metal elements selected from Ga, Al, and In from a viewpoint of further improving luminous efficiency. In the light-emitting element of the present invention, the ZnS crystal grains preferably include an impurity element derived from NaCl, KCl, Ag ₂ S, Ga ₂ S ₃ , Al ₂ S _3, or In ₂ S ₃ . In the light-emitting element of the present invention, the ZnS crystal grains preferably contain a Cl element that forms the donor level and a Cu element that forms the acceptor level, or a Cu element and an Ag element. In the light-emitting element of the present invention, the distance between the pair of electrodes is preferably 3 to 30 times the average crystal grain size of the ZnS crystal grains. In the light emitting device of the present invention, the average crystal grain size of the ZnS crystal grains is preferably 0.5 μm to 5 μm.

  Moreover, in the light emitting element of this invention, it is preferable that a pair of electrode is a comb-tooth shape from a viewpoint of improving luminous efficiency further.

Moreover, it is preferable that the light emitting element of the present invention emits light by applying an AC voltage between the pair of electrodes. In the light-emitting element of the present invention, the light-emitting layer is formed on a substrate by electron beam evaporation, sputtering or ion plating using a sintered body of a composition containing ZnS, Cu ₂ S, and NaCl as a raw material. It is preferable that the film is formed by heat treatment. In the light-emitting element of the present invention, the light-emitting layer has an electron beam evaporation method, sputtering or ion using a sintered body of a composition containing Cu ₂ S, Ag ₂ S, NaCl, Ga ₂ S ₃ and ZnS as a raw material. A film formed on a substrate by plating is preferably formed by heat treatment.

  According to the present invention, it is possible to provide a light-emitting element having excellent luminous efficiency and a long lifetime.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratio in each drawing does not necessarily match the actual dimensional ratio.

  FIG. 1 is a schematic view of an embodiment of a light emitting device of the present invention as viewed from above. FIG. 2 is a cross-sectional view taken along the line II-II of the light emitting device shown in FIG. A light-emitting element 100 shown in FIG. 2 includes a substrate 1, a light-emitting layer 2 formed on the substrate 1, and a pair of electrodes provided on a surface 2a of the light-emitting layer 2 opposite to the surface in contact with the substrate 1. 3 and 4 are provided. As shown in FIG. 1, the electrodes 3 and 4 are each connected to an external power source 5.

  As the substrate 1, when light emitted from the light emitting layer 2 is extracted from the substrate side, for example, a translucent substrate such as a quartz substrate, a glass substrate, or a ceramic substrate can be used. Further, an insulating substrate such as low alkali glass that is generally used for liquid crystal displays or the like can be used. In the light-emitting element 100, when light emitted from the light-emitting layer 2 is extracted from the side opposite to the substrate, the substrate 1 does not need to be transparent, and can be an opaque substrate such as an alumina substrate.

The light emitting layer 2 includes semiconductor polycrystal and a compound having a composition different from that of the semiconductor polycrystal, which exists at the crystal grain boundary of the semiconductor polycrystal. Examples of the semiconductor polycrystal include II-VI group compound semiconductors: (Zn, Cd, Hg) (O, S, Se, Te) combinations and mixed crystals (for example, ZnCdSe). Of these, ZnS is preferred. The compound having a composition different from that of the semiconductor polycrystal is preferably a compound capable of forming a PN junction with the semiconductor polycrystal. Specifically, for ZnO, Cu ₂ O, CuAlO ₂ , CuGaO ₂ , CuInO ₂ , SrCu ₂ O _2, etc., for ZnSe, CuGaSe ₂ , CuAlSe ₂ , CuInSe _2, etc., for ZnS Cu ₂ S, CuGaS ₂ , CuAlS ₂ , CuInS _{2 and the} like. Moreover, it is preferable that it is 90-99.95 mass%, and, as for content of the semiconductor polycrystal in the light emitting layer 2, it is more preferable that it is 95-99.8 mass%.

Moreover, when the light emitting layer 2 contains ZnS as a semiconductor polycrystal, the light emitting layer 2 has a structure in which a sulfur compound containing a copper atom is present at the crystal grain boundary of the ZnS crystal grain while containing the ZnS crystal grain. preferable. The sulfur compounds containing copper atoms, _{e.g., Cu 2 S, CuGaS 2,} CuAlS 2, CuInS 2 , and the like. Such a light-emitting layer 2 is made from, for example, a material obtained by firing a mixture of ZnS, a compound containing a copper atom, and a compound containing an impurity element that is a source of DA pair light emission as necessary. It can be formed by forming a film on the substrate 1 using a method such as beam evaporation, sputtering, or ion plating, and further performing a heat treatment. The polycrystalline ZnS concentration in the light emitting layer is preferably 96 to 99.92% by mass, and more preferably 98.4 to 99.6% by mass.

Examples of the compound containing a copper atom include Cu ₂ S, CuGaS ₂ , CuAlS ₂ , and CuInS ₂ . These compounds may be used alone or in combination of two or more.

Examples of the compound containing an impurity element that causes the DA pair emission include chlorides such as NaCl and KCl, and other compounds such as Ag ₂ S, Ga ₂ S ₃ , Al ₂ S ₃ , and In ₂ S ₃ . A phosphor powder sulfur compound is mentioned.

Further, the light emitting layer 2 will be described with reference to the drawings. Here, a ZnS pellet to which Cu ₂ S and NaCl are added is used as a raw material, a light emitting layer is formed on the substrate 1 by electron beam evaporation, and this is further heat-treated to grow a ZnS crystal to form a light emitting layer. The case of 2 will be described as an example.

FIG. 3 is a schematic cross-sectional view conceptually showing the microstructure of the light emitting layer 2 when viewed from a direction parallel to the substrate. As shown in FIG. 3, the light emitting layer 2 includes a ZnS crystal grain 20 and a crystal grain boundary 22 made of ZnS mostly containing many defects. In addition, since the ZnS crystal grains 20 have a columnar structure grown in the film thickness direction, the crystal grain boundaries 22 hardly exist in directions other than the film thickness direction of the light emitting layer 2, and in the film thickness direction of the light emitting layer 2. It exists so as to extend and fills the space between the ZnS crystal grains 20. The crystal grain boundaries 22 are mostly ZnS containing many defects, and Cu ₂ S is contained therein as a sulfur compound containing copper atoms.

In the light emitting layer 2, as ZnS crystal grains grow by heat treatment, the added NaCl Cl is replaced by the S site, Cu ₂ S Cu is replaced by the Zn site, Cl serves as a donor, and Cu serves as a donor. Acts as an acceptor. In addition, since the solid solution limit of Cu in the ZnS crystal is about 0.05 atomic%, when Cu ₂ S is added in an amount exceeding this, excess Cu is precipitated at the grain boundary 22 as Cu ₂ S crystal. To do. At this time, along with the growth of ZnS crystal grains, many defects such as microvoids and microcracks are likely to occur at the grain boundary triple points. Cu, which is an impurity element contained above the solid solution limit, also tends to be extruded to the grain boundary triple point and precipitate as Cu ₂ S crystals. Therefore, it is considered that the Cu concentration at the grain boundary triple point is higher than that of other crystal grain boundaries.

FIG. 4 is a schematic diagram conceptually showing the microstructure of the light emitting layer 2 as viewed from above the electrode side. As shown in FIG. 4, at the grain boundary of the ZnS crystal grain 20, there are a Cu ₂ S crystal-containing part 24 where Cu is present at a high concentration and a ZnS amorphous part 26 where ZnS containing many defects is mainly present. include. The Cu ₂ S crystal-containing part 24 extends from the surface 2 a opposite to the surface in contact with the substrate 1 of the light emitting layer 2 in the direction toward the substrate 1. When the electrodes are provided so as to sandwich the light emitting layer 2, the Cu ₂ S crystal-containing portion 24 may form a current path in the film thickness direction, which may cause a short circuit. However, the light emitting element 100 according to the present embodiment. Since the pair of electrodes 3 and 4 are provided on one surface of the light emitting layer 2, it is possible to sufficiently prevent a short circuit.

However, if the Cu concentration in the light emitting layer 2 is too high, the Cu ₂ S crystal-containing portion 24 increases, and as a result, an electrical path tends to be formed in a direction parallel to the substrate, and a short circuit occurs between the electrodes 3 and 4. Will be generated. On the other hand, even if the Cu concentration in the light emitting layer 2 is too low, the number of carriers injected from a Cu ₂ S crystal, which will be described later, into the ZnS crystal becomes too small, making it difficult to obtain practically sufficient light emission luminance.

  From such a viewpoint, in the present invention, the Cu concentration in the light emitting layer 2 is preferably 0.1 atomic% to 5 atomic%, more preferably 0.1 atomic% to 2.5 atomic%. Preferably, it is still more preferably 0.5 atomic% to 2.0 atomic%. If the Cu concentration is less than 0.1 atomic%, sufficient light emission luminance tends to be difficult to obtain, and if it exceeds 5 atomic%, a short circuit tends to occur.

Here, a light emission phenomenon when an AC electric field is applied between the electrodes 3 and 4 of the light emitting element 100 will be described with reference to a schematic band diagram shown in FIG. FIG. 5A shows a state in which a positive voltage is applied to the Cu ₂ S crystal precipitated at the grain boundary of the ZnS crystal grain 20 and a negative voltage is applied to the ZnS crystal, and FIG. The negative voltage is applied to the Cu ₂ S crystal precipitated at the grain boundary of the ZnS crystal grain 20, and the positive voltage is applied to the ZnS crystal.

In the state shown in FIG. 5 (a), holes are injected from the Cu ₂ S crystal into the ZnS crystal and move in the direction of the electric field in the ZnS crystal, but mostly during traveling about 1 μm in the ZnS crystal. Are trapped in a relatively deep acceptor level formed by Cu element contained in the ZnS crystal. Next, when the polarity of the electric field changes and the state shown in FIG. 5B is reached, electrons which are minority carriers are injected from the Cu ₂ S crystal into the ZnS crystal and are moved by the electric field to move the conduction band. While traveling about 1 μm in the ZnS crystal, most of the electrons are once trapped in the donor level formed by the Cl element contained in the ZnS crystal, and then the acceptor level is applied when the reverse polarity electric field is applied. Recombines with holes that were trapped in the position. And the energy lost at the time of recombination becomes blue-green light emission, and is radiated | emitted from the light emitting layer outside.

  As described above, the light-emitting element of the present invention emits light by DA pair light emission that is not substantially accompanied by non-radiative recombination. Therefore, the light-emitting element is stable despite having a polycrystalline light-emitting layer with a high defect density. In addition, highly efficient light emission is possible. On the other hand, in general, in a light emitting element such as an LED using band edge emission by recombination of carriers, since the defect level of the light emitting layer acts as a non-radiative recombination center, the light emitting layer is polycrystalline with a high defect density. A practically sufficient luminous efficiency cannot be achieved.

  The thickness of the light emitting layer 2 is preferably in the range of 0.5 μm to 2.0 μm. When the thickness of the light emitting layer 2 is less than 0.5 μm, it is difficult to obtain sufficient luminance, and when it exceeds 2.0 μm, microcracks are likely to occur or partial peeling is likely to occur.

  Moreover, in the light emitting layer 2, it is preferable that the ZnS crystal grain 20 has an average crystal grain size of 0.5 μm to 5 μm. In the present specification, the “average crystal grain size of ZnS crystal grains” refers to a diameter obtained by approximating a cut surface of a ZnS crystal grain by a circle when the light emitting layer is cut by a plane parallel to the substrate. . Specifically, it can be determined, for example, by observation with a scanning electron microscope. When the average crystal grain size of the ZnS crystal grains 20 is less than 0.5 μm, the luminance of the light emitting element tends to be low. When the average crystal grain size exceeds 5 μm, the emission start voltage varies, or the portion does not emit light locally. Luminance unevenness due to the occurrence of light emitting portions tends to occur.

  The size of the ZnS crystal grains 20 depends on the film thickness of the light emitting layer, the Cu concentration in the light emitting layer, the film forming conditions, the heat treatment conditions for growing the ZnS crystal grains, and the like. For example, the Cu concentration in the light emitting layer increases. Alternatively, when the heat treatment temperature is lowered, the size of the ZnS crystal grains 20 tends to be reduced. Therefore, the Cu concentration in the light emitting layer is preferably 5 atomic% or less, and the heat treatment for growing ZnS crystal grains is preferably performed at a temperature of 400 ° C. to 650 ° C., and preferably performed at 450 ° C. to 650 ° C. More preferred.

From the viewpoint of obtaining high luminous efficiency, it is important that the ZnS crystal grains 20 have a columnar structure in which the (111) crystal plane is oriented parallel to the substrate. In the present invention, the X-ray diffraction peak intensity attributable to the (111) crystal plane in the X-ray diffraction pattern of the light emitting layer is defined as I _(111), and the X-ray diffraction peak intensity attributable to the (110) crystal plane is defined as I _{When (110)} , the peak intensity ratio (I ₍₁₁₁₎ / I ₍₁₁₀₎ ) is preferably 10 or more, more preferably 80 or more, and even more preferably 200 or more. The X-ray diffraction pattern is measured under the conditions of CuKα, 40 kV, 30 mA, and θ-2θ interlocking. When the peak intensity ratio (I ₍₁₁₁₎ / I ₍₁₁₀₎ ) is 100 or more, a light-emitting element having a long lifetime and high light emission efficiency can be realized more easily. This is because a columnar structure ZnS crystal having an appropriate grain size is included in the light emitting layer in a high abundance ratio, so that a sulfur compound containing a copper atom existing at a crystal grain boundary and ZnS as a crystal are simulated. It is considered that a PN junction is formed, and it is considered that stable emission can be maintained by increasing the probability that electrons and holes recombine in ZnS. In addition, the sulfur compound containing a copper atom existing in the crystal grain boundary becomes a columnar shape with a high probability, can contribute to light emission more effectively, and the current path formed by the sulfur compounds is further reduced. This is considered to be the reason why

  For the electrodes 3 and 4, for example, a film of Mo, Ti, ITO, IZO or the like is formed on the light emitting layer 2 by a method such as sputtering or ion plating, and then a photolithography method or reactive ion etching (RIE). It can be formed by patterning by a method such as a method. The electrodes 3 and 4 may be provided on the substrate 1 side of the light emitting layer 2. However, the lower surface side (substrate side) of the light emitting layer formed on the substrate is usually not uniform in crystal grains. Therefore, from the viewpoint of obtaining the effect of the present invention more reliably, light emission It is preferable to form a pair of electrodes on the upper surface of the layer (the surface opposite to the substrate).

  The shape of the electrodes 3 and 4 is not particularly limited, but a comb-like electrode structure as shown in FIG. 1 is preferable. By providing an electrode having such a shape, the light emitting surface can be used efficiently, and the light emission efficiency can be further improved.

  The distance between the electrodes 3 and 4 is not particularly limited, but needs to be larger than the crystal grain size of the ZnS crystal grains 20. In the present invention, the distance between the electrodes 3 and 4 is preferably 3 to 30 times the average crystal grain size of the ZnS crystal grains 20. If the distance between the electrodes 3 and 4 is less than 3 times the average crystal grain size of the ZnS crystal grains 20, it tends to be difficult to obtain sufficient light emission efficiency. If it exceeds 30 times, the voltage required for light emission is high. As a result, this increases the cost of the drive circuit.

  Although it does not specifically limit as the power supply 5, The thing which can apply an alternating electric field is preferable.

  As described above, the light-emitting element of the present invention has excellent luminous efficiency and a long lifetime despite its very simple structure. Further, in manufacturing, a complicated process is not necessary, and it is not necessary to use an expensive transparent electrode such as ITO. Therefore, according to the present invention, it is possible to provide a planar light source that has excellent luminous efficiency, has a long lifetime, and is inexpensive.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
First, a low alkali glass substrate (125 mm × 125 mm, thickness: 0.7 mm) was prepared as a substrate, and this surface was scrubbed with a neutral detergent and further washed with isopropyl alcohol vapor. Next, the cleaned substrate was placed on the film formation substrate holder of the vapor deposition apparatus, and was evacuated until the pressure in the film formation chamber of the vapor deposition apparatus reached 2 × 10 ⁻⁴ Pa. Furthermore, the substrate temperature was raised to 180 ° C. by a resistance heating device arranged near the substrate of the vapor deposition apparatus.

Next, Cu ₂ S, NaCl, and ZnS powders having a purity of 99.9% or more were weighed in proportions of 5 mol%, 0.1 mol%, and 94.9 mol%, respectively, and these were placed in an alumina mortar. The mixture was kneaded for 30 minutes. Next, the fully kneaded powder mixed raw material was packed into a metal mold, and then pressure-molded into a 20 mmφ × 20 mm cylinder using a hydraulic molding machine. Thereafter, the pressure-mixed powder mixed raw material was placed on an alumina boat and fired at 1100 ° C. for 30 minutes in a quartz tube furnace in an argon atmosphere to produce a mixed sintered body raw material pellet. The obtained mixed sintered material raw material pellet was used as a raw material, and this was deposited on a substrate by an electron beam evaporation method to form a thin film having a thickness of 1 μm. The formed thin film is a polycrystalline thin film containing ZnS as a main component and containing Cu, Na and Cl as impurities.

By the way, in the light emitting layer which emits DA pair light emission, it is usually desirable that the donor impurity and the acceptor impurity exist in the same concentration. However, when a mixed sintered body pellet is used as a raw material to form a film by the electron beam evaporation method, the Cu concentration in the light emitting layer formed because the vapor pressure of Cu ₂ S is lower than the vapor pressure of Zn is This is about an order of magnitude lower than the Cu concentration. Therefore, in Example 1, the Cu ₂ S concentration in the raw material is set high as described above.

  Next, the film formed on the substrate was heat-treated in an Ar atmosphere at a temperature of 550 ° C. for 5 minutes using a rapid heat treatment (RTA) apparatus to grow a ZnS crystal to form a light emitting layer. By this heat treatment, the average crystal grain size of ZnS became about 1 μm. The average crystal grain size was determined by observing the surface of the light emitting layer with a scanning electron microscope.

Next, a 200 nm-thick Mo film was formed on the light-emitting layer by sputtering. Subsequently, this film is patterned into a comb shape similar to that shown in FIG. 1 by ordinary photolithography and a reactive ion etching (RIE) method using SF ₆ gas as an etchant. A pair of electrodes having a distance of 15 μm was formed. This obtained the light emitting element of Example 1.

  When an X-ray diffraction pattern (CuKα, 40 kV, 30 mA, θ-2θ interlocking) was measured for the light emitting layer of the obtained light emitting device, a strong peak was confirmed at 2θ = 28.4 to 28.6 °, and zinc blende was obtained. It was found that a ZnS crystal having a columnar structure with a (111) crystal plane oriented parallel to the substrate was formed.

Further, the peak when the X-ray diffraction peak intensity attributed to the (111) crystal plane in the X-ray diffraction pattern is I ₍₁₁₁₎ and the X-ray diffraction peak intensity attributed to the (110) crystal plane is I _(110). The intensity ratio (I ₍₁₁₁₎ / I ₍₁₁₀₎ ) was 205.

When an alternating voltage of 60 Hz and 60 V was applied between the electrodes of the obtained light emitting element, blue-green light emission having an emission spectrum shown in FIG. 6 was started, and a luminance of about 2000 cd / m ² was obtained when 100 V was applied. It was. Furthermore, when a life test was performed in which an alternating voltage of 60 Hz and 100 V was continuously applied, it was confirmed that the luminance of 1800 cd / m ² or more was maintained even after 10,000 hours.

(Examples 2 to 6)
The thicknesses of the thin films formed on the substrate were 0.3 μm, 0.5 μm, 0.7 μm, 1.5 μm, and 2.0 μm, respectively, in the same manner as in Example 1 except for the thicknesses of Examples 2 to 6. Each light emitting element was manufactured.

  An initial light emission luminance was obtained by applying an AC voltage of 60 Hz and 100 V to the obtained light emitting element. The obtained results are collectively shown in FIG. 7 as a graph showing the relationship between the thickness of the light emitting layer and the luminance. The results of Example 1 are also shown.

As shown in FIG. 7, the light emitting devices of Examples 2 to 5 in which the thickness of the light emitting layer is 0.3 μm, 0.5 μm, 0.7 μm, 1.5 μm, and 2.0 μm have high luminous efficiency. It was confirmed that In particular, it was found that high luminance of 1400 cd / m ² or more can be obtained when the thickness of the light emitting layer is 0.5 μm, 0.7 μm, 1.5 μm, and 2.0 μm.

  Furthermore, when the life test which continues applying 60Hz and 100V alternating voltage to the light emitting element of Examples 2-6 was done, all the light emitting elements maintained the brightness | luminance of 90% or more with respect to initial stage light emission brightness after 10,000 hours. It was confirmed that FIG. 8 shows the relationship between the test time and the ratio of the luminance to the initial luminance (luminance / initial luminance) as an obtained result.

(Examples 7 to 9)
The light emitting elements of Examples 7 to 9 were produced in the same manner as in Example 1 except that the heat treatment temperatures of the films formed on the substrate were 400 ° C., 450 ° C., and 650 ° C., respectively.

  An X-ray diffraction pattern (CuKα, 40 kV, 30 mA, θ-2θ interlocking) was measured for the light emitting layer of the obtained light emitting device. The obtained diffraction patterns are shown together in FIG. FIG. 9 also shows an X-ray diffraction pattern for the light-emitting layer produced in the same manner as in Example 1 except that the film formed on the substrate was not heat-treated.

Further, the peak when the X-ray diffraction peak intensity attributed to the (111) crystal plane in the X-ray diffraction pattern is I ₍₁₁₁₎ and the X-ray diffraction peak intensity attributed to the (110) crystal plane is I _(110). The intensity ratio (I ₍₁₁₁₎ / I ₍₁₁₀₎ ) was determined. The results are shown in Table 1.

  Further, for the light-emitting elements of Examples 7 to 9, the initial light emission luminance was obtained in the same manner as in Example 1, and the life test was performed. The results are shown in Table 1.

(Examples 10 to 12)
The light emitting elements of Examples 10 to 12 were produced in the same manner as in Example 1 except that the Cu ₂ S concentration in the ZnS mixed sintered body pellets was 1 mol%, 10 mol%, and 25 mol%, respectively.

The X-ray diffraction pattern (CuKα, 40 kV, 30 mA, θ-2θ interlocking) is measured for the light-emitting layer of the obtained light-emitting element, and the X-ray diffraction peak intensity due to the (111) crystal plane in the X-ray diffraction pattern is expressed as I _{( 111)} and the peak intensity ratio (I ₍₁₁₁₎ / I ₍₁₁₀₎ ) when the X-ray diffraction peak intensity attributed to the (110) crystal plane is I ₍₁₁₀₎ . The results are shown in Table 2.

  Further, for the light emitting devices of Examples 10 to 12, the initial light emission luminance was obtained in the same manner as in Example 1, and the life test was performed. The results are shown in Table 2.

(Example 13)
First, a low alkali glass substrate similar to that in Example 1 was prepared and washed in the same manner.

On the other hand, Cu ₂ S, Ag ₂ S, NaCl, Ga ₂ S ₃ and ZnS powders (all having a purity of 99.9% or more) were mixed in the composition shown in Table 3 below, and pressure was applied to 5 inches × It was molded into a shape of 15 inches × 5 mm. The molded body was fired at an Ar atmosphere, a pressure of 10 MPa, and a temperature of 1100 ° C. to produce a sintered body target as a raw material.

  Next, the sintered compact target was joined to a backing plate made of oxygen-free copper of a high frequency (13.56 MHz) magnetron sputtering apparatus (manufactured by Kurdex) using indium as a bonding agent.

Next, using the sintered compact target as a raw material, sputtering was performed under the following conditions to form a thin film having a thickness of 1 μm on the substrate.
Substrate heating temperature: 180 ° C
Gas flow rate: Ar, 150 sccm
Sputtering pressure: 0.5 Pa
High frequency power: 2.5kW

  Next, the film formed on the substrate was heat-treated in an Ar atmosphere at a temperature of 550 ° C. for 5 minutes using a rapid heat treatment (RTA) apparatus to grow a ZnS crystal to form a light emitting layer. By this heat treatment, the average crystal grain size of ZnS became about 1 μm. The average crystal grain size was determined by observing the surface of the light emitting layer with a scanning electron microscope.

Next, a 200 nm-thick Mo film was formed on the light-emitting layer by sputtering. Subsequently, this film is patterned into a comb shape similar to that shown in FIG. 1 by ordinary photolithography and a reactive ion etching (RIE) method using SF ₆ gas as an etchant. A pair of electrodes having a distance of 15 μm was formed. This obtained the light emitting element of Example 13.

Note that the light emitting layer of the light emitting element of Example 13 is a polycrystalline thin film containing ZnS as a main component and containing Cu, Na, Cl, Ag, and Ga as impurities. In addition, as ZnS crystal grains grow by heat treatment, Cl is replaced by S sites, Cu and Ag are replaced by Zn sites, and Cl functions as a donor and Cu and Ag function as acceptors. Further, excessively added Cu and Ga are precipitated as CuGaS ₂ crystals, which are chalcopyrite crystals, at the crystal grain boundaries of the ZnS crystal grains.

  When an X-ray diffraction pattern (CuKα, 40 kV, 30 mA, θ-2θ interlocking) was measured for the light emitting layer of the obtained light emitting device, a strong peak was confirmed at 2θ = 28.4 to 28.6 °, and zinc blende was obtained. It was found that a ZnS crystal having a columnar structure with a (111) crystal plane oriented parallel to the substrate was formed.

Further, the peak when the X-ray diffraction peak intensity attributed to the (111) crystal plane in the X-ray diffraction pattern is I ₍₁₁₁₎ and the X-ray diffraction peak intensity attributed to the (110) crystal plane is I _(110). The intensity ratio (I ₍₁₁₁₎ / I ₍₁₁₀₎ ) was 182.

When an alternating voltage of 60 Hz was applied between the electrodes of the obtained light emitting element, blue light emission was started from about 50 V, and a luminance of 2300 cd / m ² was obtained when 90 V was applied. The emission spectrum at this time is shown in FIG.

Furthermore, when a life test was performed in which an AC voltage of 60 Hz and 90 V was continuously applied, it was confirmed that the luminance of 2100 cd / m ² or more was maintained even after 10,000 hours.

The reason why the light emitting device of Example 13 shows higher luminous efficiency than the light emitting device of Example 1 in which Cu ₂ S is precipitated at the grain boundaries of ZnS crystal grains is considered as follows. CuGaS ₂ deposited at the grain boundaries of ZnS crystal grains is a low-resistance material having a p-type conductivity similar to Cu ₂ S, and the band gap is about 2.4 eV and 1.1 eV of Cu ₂ S. Wide compared to. Therefore, it is considered that the light emission efficiency is improved because the band offset when the junction is formed with ZnS becomes smaller and the injection efficiency of holes and electrons into ZnS becomes higher.

(Examples 14 and 15)
In the production of the sintered compact target, the same procedure as in Example 13 was performed except that 0.6 mol% of Al ₂ S ₃ and 0.6 mol% of In ₂ S ₃ were used instead of Ga ₂ S _3. The light emitting elements of Examples 14 and 15 were produced.

When an alternating voltage of 60 Hz was applied between the electrodes of the obtained light emitting device, blue light emission was started from a lower voltage of about 40 V in the light emitting device of Example 14, and a luminance of 2700 cd / m ² was obtained when 90 V was applied. It was. In the light-emitting element of Example 15, blue light emission was started at a voltage of about 60 V, and the luminance when 90 V was applied was 1800 cd / m ² .

It is the schematic which looked at one Embodiment of the light emitting element of this invention from upper direction. It is II-II arrow sectional drawing of the light emitting element shown by FIG. It is a schematic cross section which shows notionally the microstructure of the light emitting layer 2 which concerns on one Embodiment of the light emitting element of this invention. It is a schematic diagram which shows notionally the microstructure of the light emitting layer 2 which concerns on one Embodiment of the light emitting element of this invention. It is a band schematic diagram for demonstrating the light emission phenomenon which concerns on one Embodiment of the light emitting element of this invention. 6 is a graph showing an emission spectrum of the light-emitting element obtained in Example 1. FIG. It is a graph which shows the relationship between the film thickness of the light emitting layer of the light emitting element which concerns on this invention, and initial stage light emission brightness | luminance. It is a graph which shows the relationship between the test time and the ratio of the brightness | luminance with respect to initial luminance (luminance / initial luminance) in the lifetime test of the light emitting element which concerns on this invention. It is a figure which shows the X-ray-diffraction pattern of the light emitting layer of the light emitting element which concerns on this invention. FIG. 10 shows an emission spectrum of the light-emitting element obtained in Example 13.

Explanation of symbols

1 ... substrate, 2 ... light-emitting layer, 3,4 ... electrode, 20 ... ZnS crystal grains, 22 ... grain boundary, 24 ... Cu ₂ S crystal-containing unit, 26 ... ZnS amorphous portion, 100 ... light-emitting element.

Claims (13)

A substrate, a light emitting layer formed on the main surface of the substrate, and a pair of electrodes provided on the surface of the light emitting layer opposite to the surface in contact with the substrate,
The light emitting layer includes a semiconductor polycrystal including an impurity element forming a donor level and an impurity element forming an acceptor level, and a composition different from the semiconductor polycrystal, present at a crystal grain boundary of the semiconductor polycrystal And comprising
The semiconductor polycrystal is ZnS crystal grains;
Said compound having a composition different from the semiconductor polycrystal is a _{Cu 2 S, CuGaS 2, CuAlS} 2 or CuInS _2, the light emitting element. _2. The light emitting device according to claim 1 , wherein the Cu ₂ S, CuGaS ₂ , CuAlS _2, or CuInS ₂ is present extending in a direction from the surface opposite to the surface in contact with the substrate of the light emitting layer toward the substrate. The X-ray diffraction peak intensity attributed to the ZnS (111) crystal plane in the X-ray diffraction pattern of the light emitting layer is defined as I _(111), and the X-ray diffraction peak intensity attributed to the ZnS (110) crystal plane is defined as I ₍₁₁₀₎ . when the peak intensity ratio _{(I (111) / I (} 110)) is 80 or more, the light-emitting device according to claim 1 or 2. The light emitting element as described in any one of Claims 1-3 whose copper concentration in the said light emitting layer is 0.1 atomic%-5 atomic%. The light-emitting layer, Ga, including Al and at least one metallic element selected from among In, the light emitting device according to any one of claims 1-4. The ZnS crystal grains, _NaCl, KCl, containing an impurity element from the _{Ag 2 S, Ga 2 S 3} , Al 2 S 3 or _In 2 _{S 3,} light emission of any one of claims 1 to 5 element. The said ZnS crystal grain contains the Cl element which forms the said donor level, and the Cu element which forms the said acceptor level, or Cu element and Ag element, It is any one of Claims 1-6. Light emitting element. The light emitting element according to any one of claims 1 to 7 , wherein a distance between the pair of electrodes is 3 to 30 times an average crystal grain size of the ZnS crystal grains. The average crystal grain size of the ZnS crystal grains is 0.5 m to 5 m, the light emitting device according to any one of claims 1-8. The light emitting device according to any one of claims 1 to 9 , wherein the pair of electrodes has a comb shape. The light emitting element according to any one of claims 1 to 10 , wherein light is emitted by applying an alternating voltage between the pair of electrodes. The light emitting layer is formed by heat-treating a film formed on the substrate by electron beam evaporation, sputtering or ion plating using a sintered body of a composition containing ZnS, Cu ₂ S, and NaCl as a raw material. those that are light-emitting element according to any one of claims 1 to 11. The light emitting layer is formed on the substrate by electron beam evaporation, sputtering or ion plating using a sintered body of a composition containing Cu ₂ S, Ag ₂ S, NaCl, Ga ₂ S ₃ and ZnS as a raw material. and is formed by heat-treating membrane, light-emitting device according to any one of claims 1 to 12.

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