ITO substrate and preparation method thereof, organic electric pumping laser diode and preparation method and application of organic electric pumping laser diode

Abstract

The invention discloses an ITO substrate and a preparation method thereof, an organic electric pumping laser diode and a preparation method and application of the organic electric pumping laser diode. The ITO substrate comprises a light-transmitting base plate, an ITO layer, a metal layer and a light-transmitting insulating layer which are sequentially arranged in a stacked mode, the ITO layer is a patterned ITO layer, the metal layer is a patterned metal layer, the size and the pattern of the metal layer are matched with those of the ITO layer, the light-transmitting insulating layer is a patterned light-transmitting insulating layer and only covers the middle area of the metal layer, and the light-transmitting insulating layer is a patterned light-transmitting insulating layer and only covers the middle area of the metal layer. The middle area of the ITO substrate is further provided with a plurality of through holes which penetrate through the light-transmitting insulating layer and the metal layer and directly reach the surface of the ITO layer. The ITO substrate has low optical loss and high conductivity, the organic electric pumping laser diode made of the ITO substrate can achieve high-current-density injection, the performance is quite excellent, and the ITO substrate is suitable for large-scale industrial production and application.

Description

Technical Field

[0001] The invention relates to the field of semiconductor laser technology, and in particular to an ITO substrate and a preparation method thereof, an organic electric pump laser diode and a preparation method and application thereof. Background Art

[0002] Organic dye lasers have the advantages of easy adjustment of light color and simple processing, and have been widely used in military, optical, medical and other fields. Organic electrically pumped laser devices are still a difficult peak to climb in the field of organic light-emitting devices, mainly because they require the device's injection current density to reach kA / cm 2 level. However, organic materials are limited by their low thermal and electrical conductivity. When injected with such a high current density, the device will heat up severely, which will eventually seriously affect the efficiency of the device and damage the device. In addition, in electrically pumped laser devices, the ITO conductive electrode will seriously quench the laser performance of the laser material. At present, the optical loss is mainly reduced by doping SiO2 in the preparation of ITO to reduce the refractive index of the electrode, or by reducing the thickness of the ITO electrode. However, both methods will sacrifice the conductive properties of the electrode, resulting in the ITO electrode being unable to have both low optical loss and high conductivity, which will ultimately make it difficult for the device to achieve high current density injection.

[0003] Therefore, it is of great significance to develop an ITO substrate with low optical loss and high conductivity, and further prepare an organic electrically pumped laser diode with excellent performance. Summary of the invention

[0004] The purpose of the present invention is to provide an ITO substrate and a preparation method thereof, an organic electric pump laser diode and a preparation method and application thereof.

[0005] The technical solution adopted by the present invention is:

[0006] An ITO substrate comprises a light-transmitting substrate, an ITO layer, a metal layer and a light-transmitting insulating layer which are stacked in sequence; the ITO layer is a patterned ITO layer; the metal layer is a patterned metal layer whose size and pattern match those of the ITO layer; the light-transmitting insulating layer is a patterned light-transmitting insulating layer which only covers the middle area of ​​the metal layer; and a plurality of through holes which penetrate the light-transmitting insulating layer and the metal layer and directly reach the surface of the ITO layer are also arranged in the middle area of ​​the ITO substrate.

[0007] Preferably, the light-transmitting substrate is one of a white glass substrate, a quartz substrate and a sapphire substrate.

[0008] Preferably, the side of the light-transmitting substrate close to the ITO layer further comprises a distributed Bragg reflector film (DBR film).

[0009] Preferably, the thickness of the ITO layer is 15 nm to 30 nm.

[0010] Preferably, the metal layer comprises at least one of Mo, Au and Al.

[0011] Preferably, the thickness of the metal layer is 60 nm to 250 nm.

[0012] Preferably, the light-transmitting insulating layer is composed of at least one of silicon dioxide, polyimide, polystyrene and silicon nitride.

[0013] Preferably, the thickness of the light-transmitting insulating layer is 0.6 μm to 2 μm.

[0014] A method for preparing the ITO substrate as described above comprises the following steps:

[0015] 1) Depositing ITO on a single side of a light-transmitting substrate by magnetron sputtering, and then performing photolithography to form an ITO layer;

[0016] 2) depositing electrode metal on the surface of the ITO layer by magnetron sputtering, and then performing photolithography to form a metal layer;

[0017] 3) A light-transmitting insulating material is coated on the surface of the metal layer by a coating method, and then photolithography is performed to form a light-transmitting insulating layer, thereby obtaining an ITO substrate.

[0018] An organic electrically pumped laser diode comprises a substrate, an organic light-emitting material layer and a metal electrode layer which are stacked in sequence, and the substrate is the above-mentioned ITO substrate.

[0019] Preferably, the organic light-emitting material layer comprises a hole transport layer, a light-emitting layer and an electron transport layer which are stacked in sequence.

[0020] Preferably, the components of the hole transport layer include at least one of NPB (N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine), TCTA (4,4',4"-tri(carbazole-9-yl)triphenylamine), TAPC (4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline]), MEOTPD (N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine), and F4-TCNQ (2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane; the abbreviation can also be "TCNQF4").

[0021] Preferably, the hole transport layer has a thickness of 10 nm to 40 nm.

[0022] Preferably, the components of the light-emitting layer include at least one of AND (9,10-di(2-naphthyl)anthracene), C545T (10-(2-benzothiazole)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyranyl[6,7,8-ij]quinolizin-11-one; commonly known as "coumarin 545T"), DCJTI (2-[2-isopropyl-6-[2-(2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H-benzo[ij]quinolizin-9-yl)vinyl]-4H-pyran-4-ylidene]malononitrile), DPAVBI (4,4'-bis[4-(di-p-tolylamino)phenylvinyl]biphenyl), and BSBCz (4,4'-bis[(9-carbazolyl)phenylvinyl]biphenyl).

[0023] Preferably, the thickness of the light-emitting layer is 20 nm to 30 nm.

[0024] Preferably, the components of the electron transport layer include at least one of Bebq2 (bis(10-hydroxybenzo[h]quinoline)beryllium), Alq (8-hydroxyquinoline aluminum), Tmpypb (1,3,5-tris(3-pyridyl-3-phenyl)benzene), TPBi (2,2',2"-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole)), BPhen (4,7-diphenyl-1,10-phenanthroline), and Liq (8-hydroxyquinoline lithium).

[0025] Preferably, the thickness of the electron transport layer is 10 nm to 30 nm.

[0026] Preferably, the metal electrode layer comprises at least one of Ag, Mo, Au and Al.

[0027] Preferably, the thickness of the metal electrode layer is 60 nm to 250 nm.

[0028] A method for preparing the organic electrically pumped laser diode as described above comprises the following steps:

[0029] a) using an evaporation method to evaporate an organic light-emitting material on a surface of an ITO substrate to form an organic light-emitting material layer;

[0030] b) Using an evaporation method to evaporate electrode metal on the surface of the organic light-emitting material layer to form a metal electrode layer, thereby obtaining an organic electrically pumped laser diode.

[0031] A display device comprises the above-mentioned organic electric pumping laser diode.

[0032] The beneficial effects of the present invention are as follows: the ITO substrate of the present invention has both low optical loss and high conductivity, and the organic electrically pumped laser diode made therefrom can achieve high current density injection, has excellent performance, and is suitable for large-scale industrial production and application.

[0033] Specifically:

[0034] 1) The thickness of the ITO layer in the ITO substrate of the present invention is only 15nm to 30nm, which is much lower than that of the conventional ITO electrode (the thickness of the ITO layer is greater than 100nm), which can greatly reduce the quenching of the light in the OLED device by the ITO layer, thereby significantly improving the luminous efficiency of the OLED device;

[0035] 2) The ITO substrate of the present invention uses metal wires (metal layers), which can effectively reduce the overall capacitance and resistance of the OLED device, thereby achieving injection of higher current density;

[0036] 3) The organic electrically pumped laser diode of the present invention uses a metal with high thermal conductivity as the outer wall of the OLED light-emitting pixel, which can greatly reduce the heat generated by the OLED device when driven at a high current density;

[0037] 4) The organic electrically pumped laser diode of the present invention can be used in high-definition OLED display screens (mobile / TV), AR, VR and other display devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a schematic diagram of the structure of the ITO substrate in the present invention.

[0039] Figure 2 It is a flow chart of the preparation of the ITO substrate in the present invention.

[0040] Figure 3 It is a schematic diagram of the structure of the organic electrically pumped laser diode in the present invention.

[0041] Description of the symbols in the accompanying drawings: 10, light-transmitting substrate; 20, ITO layer; 30, metal layer; 40, light-transmitting insulating layer; 50, organic light-emitting material layer; 60, metal electrode layer.

[0042] Figure 4 This is the current density-brightness-voltage relationship curve of the organic electrically pumped laser diode in Example 1.

[0043] Figure 5 This is a diagram of the electrical pulse signal of the organic electrically pumped laser diode in Example 1.

[0044] Figure 6 This is the current density-brightness-voltage relationship curve of the organic electrically pumped laser diode in Example 2.

[0045] Figure 7 This is the threshold curve of edge emission amplified spontaneous emission of the organic electrically pumped laser diode in Example 2.

[0046] Figure 8 It is the threshold curve of edge emission amplified spontaneous emission of the organic electrically pumped laser diode in the comparative example. DETAILED DESCRIPTION

[0047] The present invention will be further explained and illustrated below in conjunction with specific embodiments.

[0048] Embodiment 1:

[0049] An ITO substrate (structural schematic diagram as shown Figure 1 As shown), it consists of a light-transmitting substrate 10, an ITO layer 20, a metal layer 30 and a light-transmitting insulating layer 40, and a plurality of through holes penetrating the light-transmitting insulating layer 40 and the metal layer 30 are also provided in the middle region, which directly reach the surface of the ITO layer 20; the light-transmitting substrate 10, the ITO layer 20, the metal layer 30 and the light-transmitting insulating layer 40 are stacked in sequence from bottom to top; the ITO layer 20 is a patterned ITO layer; the metal layer 30 is a patterned metal layer, and the size and pattern match the ITO layer 20; the light-transmitting insulating layer 40 is a patterned light-transmitting insulating layer, which only covers the middle region of the metal layer 30; the light-transmitting substrate 10 is a quartz substrate with a thickness of 500 μm; the thickness of the ITO layer 20 is 20 nm; the metal layer 30 is a Mo layer with a thickness of 200 nm; the light-transmitting insulating layer 40 is a polyimide layer with a thickness of 1 μm.

[0050] The preparation method of the above-mentioned ITO substrate is as follows (preparation flow chart as shown in Figure 2 shown):

[0051] 1) A 20 nm thick ITO film (square resistance of about 300 Ω / □) was deposited on a single side of a quartz substrate by magnetron sputtering, with a sputtering power of 850 W and a deposition time of 20 s, followed by annealing at 200° C. for 30 min, then washed with deionized water and dried in an oven at 85° C., then spin-coated with 1 μm thick Ruihong RZJ-304 photoresist on the surface of the ITO film, then placed on a hot plate and baked at 100° C. for 90 s, then subjected to laser direct writing exposure at 40 mjIGH exposure measurement, then placed in a 2.38% mass fraction tetramethylammonium hydroxide (TMAH) solution and deionized water for 60 s each, then placed on a hot plate for annealing at 120° C. for 120 s, then placed in a 1.0 mol / L oxalic acid solution for etching for 150 s, then stripped with a 1.5 mol / L stripping solution for 10 min to form an ITO layer;

[0052] 2) A Mo film with a thickness of 200 nm (square resistance <0.6Ω / □) is deposited on the surface of the ITO layer by magnetron sputtering, the sputtering power is 500W, the deposition rate is 0.29nm / s, and then washed with deionized water and placed in an oven at 85°C for drying, and then a 1μm thick Ruihong RZJ-304 photoresist is spin-coated on the surface of the Mo film, and then placed on a hot plate for baking at 100°C for 90s, and then laser direct writing exposure is performed under 40mjIGH exposure measurement, and then placed in a tetramethylammonium hydroxide solution with a mass fraction of 2.38% and deionized water for development for 60s respectively, and then placed on a hot plate for annealing at 120°C for 120s, and then placed in nitric acid with a mass fraction of 68% for room temperature etching for 60s, and then a stripping solution with a concentration of 1.5mol / L is used to remove the glue for 10min to form a metal layer;

[0053] 3) A polyimide film with a thickness of 1 μm is coated on the surface of the metal layer by a spin coating method, and then the film is washed with deionized water and dried in an oven at 85° C., and then a Toray DL 1000C photoresist with a thickness of 2 μm is spin coated on the surface of the polyimide film, and then the film is placed on a hot plate and baked at 120° C. for 120 seconds, and then laser direct writing exposure is performed under an exposure meter of 130 mjIGH, and then the film is placed in a tetramethylammonium hydroxide solution with a mass fraction of 2.38% and deionized water for development for 60 seconds each, and then the film is placed in an oven and baked at 250° C. for 60 minutes, and then the film is placed in a nitric acid with a mass fraction of 68% and etched at room temperature for 60 seconds, and then a stripping solution with a concentration of 1.5 mol / L is used to remove the glue for 10 minutes to form a light-transmitting insulating layer, thereby obtaining an ITO substrate.

[0054] An organic electrically pumped laser diode (schematic diagram as shown in Figure 3 As shown), it is composed of the ITO substrate, the organic light-emitting material layer 50 and the metal electrode layer 60 in this embodiment; the ITO substrate, the organic light-emitting material layer 50 and the metal electrode layer 60 are stacked in sequence from bottom to top; the organic light-emitting material layer 50 is composed of a hole transport layer, a light-emitting layer and an electron transport layer stacked in sequence from bottom to top; the hole transport layer has a thickness of 40nm, and is composed of a MEOTPD film with a thickness of 10nm and a MEOTPD:F4-TCNQ film with a thickness of 30nm (the mass ratio of MEOTPD and F4-TCNQ is 94:6) stacked in sequence from bottom to top; the light-emitting layer is an ADN:DPAVBI film with a thickness of 30nm (the mass ratio of ADN and DPAVBI is 94:6); the electron transport layer is a Bebq2:Liq film with a thickness of 30nm (the mass ratio of Bebq2 and Liq is 9:1).

[0055] The preparation method of the organic electric pumped laser diode is as follows:

[0056] a) Wash the above ITO substrate with deionized water and dry it, then place it in a vacuum chamber with a degree of <4×10 -4The evaporation chamber of Pa sequentially evaporates a 10 nm thick MEOTPD film, a 30 nm thick MEOTPD:F4-TCNQ film (the mass ratio of MEOTPD to F4-TCNQ is 94:6), a 30 nm thick ADN:DPAVBI film (the mass ratio of ADN to DPAVBI is 94:6), and a 30 nm thick Bebq2:Liq film (the mass ratio of Bebq2 to Liq is 9:1) on the surface of the ITO substrate (the side where the light-transmitting insulating layer is located) by an evaporation method, and the evaporation rate is 0.1 nm / s to form an organic light-emitting material layer;

[0057] b) A 100 nm thick Ag film is deposited on the surface of the organic light-emitting material layer (the surface of the Bebq2:Liq film) by evaporation at a rate of 0.1 nm / s to form a metal electrode layer, which is then placed in a nitrogen-filled glove box and encapsulated using a glass sheet to obtain an organic electric pumped laser diode.

[0058] Performance Test:

[0059] The pulse signal generator AVTECH / AVR-3H3-B is used to generate an electric pulse with a pulse width of 80ns for the organic electro-pumped laser diode. The luminous brightness of the device is collected by a photomultiplier tube and corrected with the real brightness collected by a brightness meter CS2000. The electric pulse signal of the device is collected by an oscilloscope. The current density-brightness-voltage relationship curve of the device obtained by the test is shown in the figure. Figure 4 As shown, the electrical pulse signal of the device is Figure 5 shown.

[0060] Depend on Figure 4 and Figure 5 It can be seen that the organic electrically pumped laser diode can achieve 5kA / cm under the drive of 80ns electric pulse. 2 The current density was injected and the brightness was 6×10 6 cd / m 2 The light output is excellent.

[0061] Embodiment 2:

[0062] An organic electrically pumped laser diode is identical to the organic electrically pumped laser diode in Example 1, except that the structure of the organic light-emitting material layer is adjusted to "a Yb film with a thickness of 100 nm, a BSBCz:Cs2CO3 film with a thickness of 300 nm (the mass ratio of BSBCz to Cs2CO3 is 2:1), a BSBCz film with a thickness of 2000 nm, a BSBCz:MoO3 film with a thickness of 300 nm (the mass ratio of BSBCz to MoO3 is 1:0.2) and a HAT-CN film with a thickness of 100 nm" and the thickness of the Ag film is adjusted to "1500 nm".

[0063] Performance test (test method is the same as in Example 1):

[0064] The current density-brightness-voltage relationship curve of organic electrically pumped laser diode is as follows: Figure 6 shown.

[0065] Depend on Figure 6 It can be seen that the organic electrically pumped laser diode can achieve 4kA / cm under the drive of 80ns electric pulse. 2 The current density was injected and the brightness was 1.8×10 7 cd / m 2 The light output is excellent.

[0066] Comparative Example:

[0067] An organic electric pumping laser diode is completely the same as the organic electric pumping laser diode in Example 2 except that the thickness of the ITO layer is adjusted from "20nm" to "100nm".

[0068] Performance Test:

[0069] A spectral physics femtosecond laser was used to pump a laser with a pulse width of 100 fs and a wavelength of 370 nm. The laser was then shaped into a 4 mm × 0.5 mm stripe shape by a convex cylindrical mirror and then projected onto a test sample (the organic electrically pumped laser diode in Example 2 and the comparative example). The edge emission spectrum of the test sample was then guided by an optical fiber to an OCEANVIEW65 PRO spectrometer. The threshold curve of the edge emission amplified spontaneous emission of the organic electrically pumped laser diode obtained by the test was as shown in FIG. Figure 7 and Figure 8 shown.

[0070] Depend on Figure 7 and Figure 8 It can be seen that the threshold of the edge-emission amplified spontaneous emission of the organic electrically pumped laser diode in Example 2 is 3.8 μJ / cm 2 , while the organic electro-pumped laser diode in the comparative example reached 9.2 μJ / cm 2The increase in the thickness of the ITO layer brings about serious quenching of amplified spontaneous emission, which eventually causes the threshold of the device to increase by nearly 3 times. It can be seen that the ITO substrate in the present invention has the advantage of low optical loss.

[0071] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An ITO substrate, characterized in that: The composition includes a light-transmitting substrate, an ITO layer, a metal layer and a light-transmitting insulating layer which are stacked in sequence; the ITO layer is a patterned ITO layer; the metal layer is a patterned metal layer, and the size and pattern match the ITO layer; the light-transmitting insulating layer is a patterned light-transmitting insulating layer, which only covers the middle area of ​​the metal layer; the middle area of ​​the ITO substrate is also provided with a plurality of through holes which penetrate the light-transmitting insulating layer and the metal layer and directly reach the surface of the ITO layer.

2. The ITO substrate according to claim 1, characterized in that: The light-transmitting substrate is one of a white glass substrate, a quartz substrate, and a sapphire substrate; the components of the metal layer include at least one of Mo, Au, and Al; and the components of the light-transmitting insulating layer include at least one of silicon dioxide, polyimide, polystyrene, and silicon nitride.

3. The ITO substrate according to claim 1 or 2, characterized in that: The thickness of the ITO layer is 15 nm to 30 nm.

4. The ITO substrate according to claim 1 or 2, characterized in that: The thickness of the metal layer is 60nm to 250nm; The thickness of the light-transmitting insulating layer is 0.6 μm to 2 μm.

5. A method for preparing an ITO substrate as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: 1) Depositing ITO on a single side of a light-transmitting substrate by magnetron sputtering, and then performing photolithography to form an ITO layer; 2) depositing electrode metal on the surface of the ITO layer by magnetron sputtering, and then performing photolithography to form a metal layer; 3) A light-transmitting insulating material is coated on the surface of the metal layer by a coating method, and then photolithography is performed to form a light-transmitting insulating layer, thereby obtaining an ITO substrate.

6. An organic electrically pumped laser diode, characterized in that: The composition comprises a substrate, an organic light-emitting material layer and a metal electrode layer which are stacked in sequence; the substrate is the ITO substrate as claimed in any one of claims 1 to 4.

7. The organic electrically pumped laser diode according to claim 6, characterized in that: The organic light-emitting material layer comprises a hole transport layer, a light-emitting layer and an electron transport layer which are stacked in sequence.

8. The organic electrically pumped laser diode according to claim 7, characterized in that: The components of the hole transport layer include at least one of NPB, TCTA, TAPC, MEOTPD, and F4-TCNQ; the components of the light-emitting layer include at least one of AND, C545T, DCJTI, DPAVBI, and BSBCz; the components of the electron transport layer include at least one of Bebq2, Alq, Tmpypb, TPBi, BPhen, and Liq.

9. A method for preparing an organic electrically pumped laser diode as claimed in any one of claims 6 to 8, characterized in that: The following steps are involved: a) using an evaporation method to evaporate an organic light-emitting material on a surface of an ITO substrate to form an organic light-emitting material layer; b) Using an evaporation method to evaporate electrode metal on the surface of the organic light-emitting material layer to form a metal electrode layer, thereby obtaining an organic electrically pumped laser diode.

10. A display device, characterized in that: The organic electrically pumped laser diode comprises the organic electrically pumped laser diode according to any one of claims 6 to 8.

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