CN102222774A - Organic or inorganic electroluminescent device, anode of device and manufacturing method of anode - Google Patents
Organic or inorganic electroluminescent device, anode of device and manufacturing method of anode Download PDFInfo
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- CN102222774A CN102222774A CN2010101458979A CN201010145897A CN102222774A CN 102222774 A CN102222774 A CN 102222774A CN 2010101458979 A CN2010101458979 A CN 2010101458979A CN 201010145897 A CN201010145897 A CN 201010145897A CN 102222774 A CN102222774 A CN 102222774A
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Abstract
The invention provides an organic or inorganic electroluminescent device, an anode of the device and a manufacturing method of the anode, belonging to the field of organic or inorganic electroluminescent devices. A metal and a metal silicide layer are connected with a polycrystalline silicon layer in parallel so as to strengthen the current conductivity, and a composite film of nanoscale polycrystalline silicon and metal silicide is taken as the anode of the luminescent device, thus solving the problems that a common monocrystalline silicon anode absorbs visible light strongly and the square resistance is too large when a nanoscale polycrystalline silicon film is taken as the anode. The composite anode of the nanoscale polycrystalline silicon and the metal silicide has the characteristics of good transmission of light and electrical conductivity, adjustable work functions and hole injection, simple technology, low cost and good stability. The anode is applied to film luminescent device fields such as organic LED (light-emitting diode) displays and the like and is likely to be used to optical detection and photocell devices further.
Description
Technical field
The present invention relates to organic or inorganic electroluminescence field, be specifically related to a kind of nano thickness polysilicon of organic or inorganic film light electronics device and metal silicide laminated film as printing opacity anode and preparation method thereof.
Background technology
Present opto-electronic device development is very fast, and organic electroluminescence device begins to enter to be commercially produced.Electrode performance is very important for the effect of opto-electronic device, electrode for exiting surface requires to have good printing opacity and conductivity, the organic electroluminescence device anode also need be regulated the resistivity of electrode, and the control hole current satisfies the requirement that charge carrier injects balance, obtains high luminous efficiency.ITO electrode commonly used at present has good light transmittance and stability, but uncontrollable hole injection current, the technology relative complex, finished product is also higher.P type single crystal silicon has many advantages as the anode of organic electroluminescent, and the resistivity by regulating silicon can cause the decline of luminous efficiency at inner control hole injection current on a large scale but anode substrate has strong absorption to visible light.The nano thickness polysilicon membrane can significantly reduce visible light intensity absorption, but square resistance is too big, generally much larger than 10
4Ω/ causes series resistance and loss to increase.
Summary of the invention
The purpose of this invention is to provide a kind of ultra-thin anode material that is used for film light electronics devices such as organic light emitting diode display, and the preparation method of this thin film positive pole.Thin film positive pole of the present invention possesses that excellent conducting performance, visible light wave range lowly absorb, square resistance is adjustable, chemical property is stable, technology is simple, crystallization temperature is low, material and all lower characteristics of technology cost.
Technical scheme of the present invention is as follows:
A kind of anode of organic or inorganic electroluminescent device is characterized in that: described anode is the composite material of polysilicon and metal silicide, and this thickness of composite material is 5nm-100nm.
Described composite material can contain the metallic element of trace.
A kind of organic or inorganic electroluminescent device comprises anode, luminescent layer and negative electrode, it is characterized in that: described anode is the composite material of polysilicon and metal silicide, and this thickness of composite material is 5nm-100nm.
The luminescent layer of device is a kind of of macromolecular compound, metal complex, micromolecule organic fluorescent compounds or phosphorescent compound; Negative electrode adopts aluminium, calcium, magnesium or other low workfunction metal, or these low workfunction metal and alloy silver-colored, other noble metal.
Between anode and luminescent layer, add hole transmission layer; Or between negative electrode and luminescent layer, add electron transfer layer; Or between anode and luminescent layer, add hole transmission layer, between negative electrode and luminescent layer, add electron transfer layer.
A kind of method for preparing composite anode materials, its step is as follows:
1) plated metal and P type amorphous silicon each one or more layers successively on transparent substrates; Or be metal and P type amorphous silicon mixed deposit one deck, the crystallization of described metal pair P type amorphous silicon has induction;
2) under 400 ℃ of-800 ℃ of nitrogen protection conditions, carry out the annealing induced crystallization and handled 5-300 minute, form P type polysilicon and metal silicide composite material.
The metal level gross thickness that deposits described in the step 1) is 1nm-10nm, and P type amorphous silicon layer gross thickness is 5nm-50nm.
The volume ratio of metal described in the step 1) and P type amorphous silicon was from 1: 100 to 75: 100.
Described metal includes but not limited to any one among Fe, Au, Ni, Al, Ti, the Pt.
The employing of deposition described in step 1) physical vapour deposition (PVD) includes but not limited to any one in electron beam evaporation, magnetron sputtering, the laser beam evaporation; Or the employing chemical vapour deposition (CVD) includes but not limited in chemical vapour deposition (CVD), the plasma reinforced chemical vapour deposition any one.
Above-mentioned polysilicon/metal silicide composite anode the rete that is used for the film light electronics device of visible light frequency band is considered light transmittance and electric conductivity, and gross thickness is controlled at about 20nm usually.
Principle of the present invention is, be deposited on metal and amorphous silicon chemical combination under certain hot conditions on the transparent substrates, form metal silicide, along with the silicone content increase of dissolving in the metal reaches capacity, silicon in the metal silicide can be separated out crystallization and be formed polysilicon, has amorphous silicon simultaneously and continues to dissolve in the metal and separate out, makes the amorphous silicon membrane of deposition progressively be converted into polysilicon film, the polysilicon that crystallization forms is born the function that the hole is provided, and is luminescent device p type island region territory injected hole.Simultaneously, but the conduction of current of the metal silicide thin layer auxiliary electrode that forms in the annealing crystallization, and the conduction of current humidification is fairly obvious when membrane electrode thickness is extremely thin, significantly reduces the pressure drop and the loss of electrode.The square resistance of the polysilicon electrode of 20nm all surpasses 10 usually
4Ω/, composite anode materials can be much smaller than the resistivity of polysilicon anode, and square resistance can be controlled in 1000 Ω/below the usually.
In the composite anode materials preparation, very most of metal all is converted into metal silicide, also has the small part metallic element to stay in the composite material, and metal element content is no more than 10% of whole composite anode materials in the composite anode.
As shown in Figure 1, polysilicon and silicide composite anode preparation method are plated metal and P type amorphous silicons each one or more layers successively on transparent substrates; Or be metal and P type amorphous silicon mixed deposit one deck, by selecting to induce metal and changing component ratio and thickness between metal and the silicon, adjust the condition of annealing crystallization simultaneously, the square resistance adjustable range can be 30 Ω/ to 10
4Ω/.
Be 20nm left and right sides polysilicon/nickel silicide composite anode for example for thickness, at first deposit the amorphous silicon layer about one deck 2nm nickel dam and 20nm, after the annealing crystallization, P type polysilicon layer is about 1: 3 with the thickness ratio of nickel silicide layer in the anode, be that polysilicon layer is 5nm, the nisiloy compound is that 15nm is thick, and square resistance is about 450 Ω/.Organic film luminescent device shown in the corresponding diagram 2, with instantiation explanation, concrete structure (from bottom to top successively) is: Al/glass (substrate)/p-Si:Ni/NPB/CBP:(acac)
2Ir (ppy)/Bphen/Bphen:Cs
2CO
3/ Sm/Au, its device electroluminescence can obtain to be up to the luminous efficiency of 60lm/W.The brightness that Figure 3 shows that its organic film luminescent device characteristics of luminescence of reflection is with the change in voltage curve.
Polysilicon and silicide laminated film anode have good light transmittance, and especially this anode light absorption of infra-red range is very little, help luminescent device and improve light extraction efficiency, and visible light transmittance rate is near 60%, and the infra-red range light transmittance reaches 80%.Chemistry that composite anode is stable and electrical properties; can effectively protect organic luminescent device; stop the organic material oxidation and degenerate; and improve the above-mentioned luminous efficiency that goes out optical device also being easy on transparent substrates deposition one reflective film on the electroluminescent device, or further be processed to form the micro-cavity structure device.Therefore polysilicon and silicide composite anode are a kind ofly to possess major advantages such as low light absorption, advantages of excellent stability, cost be low, and have the novel electrode material of the function admirable of favorable conductive characteristic concurrently.Anode material not only can be applicable to thin-film light emitting devices field such as organic light emitting diode display, but also can be applicable to optical detection and photovoltaic devices aspect.
Description of drawings
Fig. 1 is that three kinds of composite anode thin film deposition structural representations: 1 (a) is two-layer depositional fabric, and 1 (b) is multilayer alternating deposit structure, and 1 (c) is individual layer codeposition structure;
Fig. 2 is for using the organic film luminescent device structural representation of nano thickness polysilicon/metal silicide anode;
Fig. 3 uses the organic film luminescent device luminosity of nano thickness polysilicon/metal silicide anode with the change in voltage curve chart;
Fig. 4 is the square resistance of polysilicon in the example 1/nickel silicide composite anode and the graph of a relation of nickel layer thickness and crystallization temperature;
Fig. 5 is the graph of a relation of polysilicon in the example 1/nickel silicide composite anode mobility and nickel layer thickness and crystallization temperature;
Fig. 6 be in the example 2 visible light transmissivity with the change curve of nickel content.
Among Fig. 1,1-transparent substrates, 2-amorphous silicon layer, 3-metal level, 4-amorphous silicon and metal mixed layer.
Embodiment
Below in conjunction with the invention will be further described by embodiment, but the present invention is not limited to following examples.
Example 1: on quartzy transparent substrates, adopt magnetron sputtering technique to deposit double-layer films respectively, ground floor is with the thick silicon thin film of P type silicon target deposition 20nm, and the second layer uses that nickel target deposit thickness is 0.5,1,2,4,8 respectively, the metallic film of 12nm.Deposition materials purity is more than 99.99%, and the carrier concentration of silicon materials is from 10
-3Ω cm, the deposition vacuum chamber background vacuum pressure is better than 5 * 10
-5Pa.Sample behind the deposit film will carry out the annealing induced crystallization under the nitrogen protection condition of purity 99.999%, treatment temperature can be 540 ℃, 600 ℃ or 800 ℃, 5 minutes time.Finished product after the annealing is polysilicon/nickel silicide film, its square resistance scope 8600 Ω/ to 30 Ω/.Shown in Figure 4 corresponding under different nickel deposition thickness and the revulsive crystallization temperature conditions in this example, the concrete change curve of polysilicon/nickel silicide composite anode square resistance, bigger plated metal layer thickness and higher anneal temperature can reduce the square resistance of composite anode.Figure 5 shows that polysilicon/nickel silicide composite anode carrier mobility is with different nickel deposition thickness and revulsive crystallization variation of temperature curve.Improving annealing temperature can increase the ability of composite anode carrier transport.But increase with metallic nickel content, carrier mobility is not dull increasing, and is subjected to the influence of polysilicon crystallization state, metal silicide content and metal element content in the composite anode and presents fluctuation.
Example 2: on transparent substrates such as glass, vitreous silica and crystal, adopt magnetron sputtering technique to deposit three-layer thin-film respectively, first and third layer is used P type silicon target deposition to be the thick silicon thin film of 8-10nm, and the second layer uses the thick thin nickel metal film of nickel target deposition 1.5-3nm.Deposition materials purity is more than 99.99%, and the carrier concentration of silicon materials is from 10
-3Ω cm, the deposition vacuum chamber background vacuum pressure is better than 5 * 10
-5Pa.Sample behind the deposit film will carry out the annealing induced crystallization under the nitrogen protection condition of purity 99.999%, 540 ℃ of treatment temperatures, 5 minutes time.Finished product square resistance after the annealing is 450 Ω/, visual transparency nearly 50%.Fig. 6 reflects that when only increasing nickel deposition thickness the visible light transmittance rate of polysilicon/nickel silicide composite anode will decrease.Higher nickel content reduces that to crystallization, the square resistance of amorphous silicon great role is arranged, but also influences the light transmittance of composite anode simultaneously.
Example 3: on transparent substrates such as glass, vitreous silica and crystal, adopt electron beam evaporation to deposit double-layer films respectively, ground floor uses nickel or the thick metallic film of aluminium source evaporation 1.5-3nm, and the second layer uses the source hydatogenesis of P type silicon to be the thick amorphous silicon membrane of 20nm.Deposition materials purity is more than 99.99%, and the carrier concentration of silicon materials is from 10
-3Ω cm, the deposition vacuum chamber background vacuum pressure is better than 5 * 10
-4Pa.Sample behind the deposit film will carry out the annealing induced crystallization under the nitrogen protection condition of purity 99.999%, 540 ℃ of treatment temperatures, 5 minutes time, form polysilicon/nickel silicide film or polysilicon/aluminum silicide film.
Example 4: on transparent substrates such as glass, vitreous silica and crystal; the thick Al of thermal evaporation one deck 8nm at first; then adopt plasma-enhanced CVD deposition one deck 20nm polycrystal silicon film of being altogether unjustifiable; reacting gas adopts silane; dilute with high-purity Ar gas; sample behind the deposit film will the high pure nitrogen protective condition under carry out the annealing induced crystallization, 550 ℃ of treatment temperatures, 10 minutes time, form polysilicon/aluminum silicide film.
In the above embodiment of the present invention, can be according to the injection carrier concentration of anode and the needs of light transmittance, change select for use induce metal and metal and amorphous silicon thickness, structure.Except that Ni, Al, can also be Fe, Au, Ti, Pt as metal.
In addition, the volume ratio of metal and P type amorphous silicon was from 1: 100 to 75: 100.
In addition, under 400 ℃ of-800 ℃ of nitrogen protection conditions, but carried out annealing induced crystallization processing time 5-300 minute.
Above-described embodiment is used to limit the present invention, and any those skilled in the art without departing from the spirit and scope of the present invention, can make various conversion and modification, so protection scope of the present invention is looked the claim scope and defined.
Claims (10)
1. the anode of an organic or inorganic electroluminescent device, it is characterized in that: described anode is the composite material of polysilicon and metal silicide, this thickness of composite material is 5nm-100nm.
2. anode as claimed in claim 1 is characterized in that: described composite material contains metallic element.
3. an organic or inorganic electroluminescent device comprises anode, luminescent layer and negative electrode, it is characterized in that: described anode is the composite material of polysilicon and metal silicide, and the thickness of described composite material is 5nm-100nm.
4. device as claimed in claim 3 is characterized in that: described composite material contains metallic element.
5. as claim 3 or 4 described devices, it is characterized in that: the luminescent layer of described device is a kind of of macromolecular compound, metal complex, micromolecule organic fluorescent compounds or phosphorescent compound; Negative electrode adopts aluminium, calcium, magnesium or other low workfunction metal, or these low workfunction metal and alloy silver-colored, other noble metal.
6. one kind prepares the method for anode material according to claim 1, and its step is as follows:
1) plated metal and P type amorphous silicon each one or more layers successively on transparent substrates; Or be metal and P type amorphous silicon mixed deposit one deck, the crystallization of described metal pair P type amorphous silicon has induction;
2) under 400 ℃ of-800 ℃ of nitrogen protection conditions, carry out the annealing induced crystallization and handled 5-300 minute, form P type polysilicon and metal silicide composite material.
7. method as claimed in claim 6 is characterized in that: the metal level gross thickness that deposits described in the step 1) is 1nm-10nm, and P type amorphous silicon layer gross thickness is 5nm-50nm.
8. as claim 6 or 7 described methods, it is characterized in that: the volume ratio of metal described in the step 1) and P type amorphous silicon was from 1: 100 to 75: 100.
9. method as claimed in claim 6 is characterized in that: described metal includes but not limited to any one among Fe, Au, Ni, Al, Ti, the Pt.
10. method as claimed in claim 6 is characterized in that: the employing of deposition described in step 1) physical vapour deposition (PVD) includes but not limited to any one in electron beam evaporation, magnetron sputtering, the laser beam evaporation; Or the employing chemical vapour deposition (CVD) includes but not limited in chemical vapour deposition (CVD), the plasma reinforced chemical vapour deposition any one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441084A (en) * | 2013-08-09 | 2013-12-11 | 如皋市日鑫电子有限公司 | Technology for manufacturing silicon slice alloy |
| CN110444671A (en) * | 2019-07-26 | 2019-11-12 | 杭州众能光电科技有限公司 | A kind of perovskite solar battery based on ultra thin p-type polysilicon film |
| US20220123190A1 (en) * | 2011-03-22 | 2022-04-21 | Micron Technology, Inc. | Vertical light emitting devices with nickel silicide bonding and methods of manufacturing |
| WO2022157907A1 (en) * | 2021-01-22 | 2022-07-28 | シャープ株式会社 | Light-emitting element, display device, and method for producing light-emitting element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060103299A1 (en) * | 2004-11-15 | 2006-05-18 | The Hong Kong University Of Science And Technology | Polycrystalline silicon as an electrode for a light emitting diode & method of making the same |
| CN1964063A (en) * | 2005-11-10 | 2007-05-16 | 香港科技大学 | Polycrystalline silicon as an electrode for a light emitting diode, method of making the same |
-
2010
- 2010-04-13 CN CN2010101458979A patent/CN102222774A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060103299A1 (en) * | 2004-11-15 | 2006-05-18 | The Hong Kong University Of Science And Technology | Polycrystalline silicon as an electrode for a light emitting diode & method of making the same |
| CN1964063A (en) * | 2005-11-10 | 2007-05-16 | 香港科技大学 | Polycrystalline silicon as an electrode for a light emitting diode, method of making the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220123190A1 (en) * | 2011-03-22 | 2022-04-21 | Micron Technology, Inc. | Vertical light emitting devices with nickel silicide bonding and methods of manufacturing |
| CN103441084A (en) * | 2013-08-09 | 2013-12-11 | 如皋市日鑫电子有限公司 | Technology for manufacturing silicon slice alloy |
| CN110444671A (en) * | 2019-07-26 | 2019-11-12 | 杭州众能光电科技有限公司 | A kind of perovskite solar battery based on ultra thin p-type polysilicon film |
| WO2022157907A1 (en) * | 2021-01-22 | 2022-07-28 | シャープ株式会社 | Light-emitting element, display device, and method for producing light-emitting element |
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Application publication date: 20111019 |