应用新型主发光体系统之高效率红色掺杂型有机电激发光元件

1、National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇1National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇 According to the different behavior of the size of the gas pressure and gas movement, vacuum divided into five levels：Pato

2、rrRough vacuumAirflow morphology：Viscous flow 1atm102 Pa7601 torrMedium vacuum Airflow morphology：Transition flow10210-1 Pa110-3torrHigh vacuum Airflow morphology：Molecular flow 10-110-5 Pa10-310-7 torrUltra-high vacuum Airflow morphology：Single-molecule movement10-510-8 Pa10-710-10 torrUltra-high v

3、acuum Airflow morphology：Single-molecule movementless 10-8 Paless 10-10 torrUnder standard atmospheric pressurePressure =1 atm =760 mmHg =760 torr = 1.013 x 105 Pa (?kg/cm2) =1013 mbar =14.7 psi =7.6 x 105 micron2National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池

4、篇 Gas molecules in the movement, each molecule before the collision to other molecules, the average walking distance is called the gas mean free path, usually represented by the symbol , unit is cm. at room temperature 20 C （The higher the temperature, molecular motion faster）PressureMean free path1

5、 x 10-3 torr5cm1 x 10-4 torr50cm1 x 10-5 torr5m1 x 10-6 torr50m1 x 10-7 torr500m1 x 10-8 torr5km1 x 10-9 torr50km1 x 10-10 torr500km3National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Rough vacuumMedium vacuum High vacuum Ultra-high vacuum Pressure (mbar)National

6、 Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇(一) Divided according to the measuring method:：1. Direct：The size of the direct measurement of the gas molecules acting on the wall or membrane of the sensing element force, reading is usually nothing to do with the gas

7、species, a rough vacuum regardless of the often used this way.2. Indirect：Characteristics of the measuring gas in a vacuum, such as thermal conductivity, viscosity, etc., to be converted into pressure, high vacuum regardless of this approach is commonly used in reading and gas type.(二) Divided on th

8、e basis of the work principle ：1. Mechanical：Wall or membrane of the sensing element to the force acting on a size to determine the size of the pressure.2. Electronic：Number of different vacuum gas molecules caused by the thermal conductivity, viscosity, ionizing the measured strength of electronic

9、signals converted into the size of the pressure. (三) Divided according to the measurement range：1. Rough vacuum: 1 atm 102 Pa, Gauge U-tube、Gauges Bourdon 。2. Medium vacuum: 10210-1 Pa, Gauge thermocouple、Gauges capacitance manometer3. High、 Ultra-high vacuum: 10-1 10-10 Pa Gauges cold cathode、Gauge

10、 ionizationNational Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Thin Film DepositionSputterEvaporationCVD(Chemical Vapor Deposition)PVD( Physical Vapor Deposition)Reactive SputterAC SputterDC Sputter6National Formosa UniversityInstitute of Electro-Optical and Mater

11、ial Science太陽能工程-太陽能電池篇First of all, the atoms reach the substrate must have a vertical movement, atoms in order to “adsorption” on a substrate. these atoms in a chemical reaction to form a thin film substrate. thin film composition atoms in the surface of the substrate diffusion movement, this phen

12、omenon is known as the adatom “Surface Migration”. when the atoms collide with each other combination of the trip atoms, Known as “nucleation”. Atoms must reach a certain size, the continuous stable growth. therefore, the small clusters will be inclined to each other polymerization, formation of a l

13、arger atoms, to cut overall energy. Atoms continue to grow will form the “island”. gaps between the nuclear island need to fill in order of atomic island junction and the formation of the entire continuous film. unable to bonding of atoms and the substrate, will be taken from the substrate surface d

14、etachment, to formation of free atoms, this step is called the atomic “desorption”.SubstrateAdsorptionChemicalreactionDesorptionSurface MigrationnucleationNational Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇8National Formosa UniversityInstitute of Electro-Optical

15、and Material Science太陽能工程-太陽能電池篇9National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇The frequency of using magnets to scan the film thickness can be controlled, scanningmore the number of film thickness and the thicker. In general, more suitable for thin film dep

16、osition conditions: high substrate temperature, low pressure, clean, smooth and non-reaction with the deposited film and the lattice size similar substrate.10National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇PVD Evaporation Vacuum evaporation Sputtering Ion depo

17、sition Ions generated heatkinetic heatThin film growth rate Can improve ( 75 m/min)Pure metal other than low (Cu：1m/min)Can improve( 25 m/min)Particle Atoms, ions Atoms, ionsAtoms, ionsDeposition uniformity if no gas mix in , and it will be worsegood，but the film thickness uneven good，but the film t

18、hickness unevenDeposition of metal YESYESYESEvaporation alloy YESYESYES11National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇PVD Evaporation Vacuum evaporation Sputtering Ion deposition Evaporation heat-resistant compounds YESYESYESParticle energy 0.10.5eV1100eV11

19、00eVThe impact of the inert gas ion usually notYes，or not because of its shapeYESMixing between the surface and layer usually notYESYESHeating (external heating)YESusually notYes and NoDeposition rate 10-9 m/sec1.6712500.1716.70.583312National Formosa UniversityInstitute of Electro-Optical and Mater

20、ial Science太陽能工程-太陽能電池篇Nature of the methodDeposition rateLarge-size controlPrecise composition controlCan be deposited materialsManufacturing cost真空蒸鍍(Evaporation)SlowPoorLessPoorPoor分子束磊晶成長(MBE)SlowPoorExcellentPoorPoor濺鍍(Sputter)BestBestBestmanyExcellent13National Formosa UniversityInstitute of E

21、lectro-Optical and Material Science太陽能工程-太陽能電池篇Thin Film DepositionCVD(Chemical Vapor Deposition)PVD( Physical Vapor Deposition)By PressureAPCVD760 torrLPCVD 10-1 torrPECVD500 mtorrBy Energy Resistance Heat Re induction Glow Discharge PhotonsBy Reactor TypeHot/Cool wall14National Formosa UniversityI

22、nstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇 (1)(1) Import the main airstream of the reactants (laminar flow (?) (2)(2) internal diffusion of reactants (3)(3) Atomic adsorption (4)(4) Surface chemical reaction (5)(5) Resultant outer diffusion and remove基板基板At High temperature At High

23、 temperature (200-500C)(200-500C)(4)main airstream(1)ReactantSiH4, H2High concent(2)internal diffusion Low concent(3) Adsorption(5) outer diffusion15Boundary layer(6)Chemical reactionNational Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇16The so-called atmospheric p

24、ressure chemical vapor deposition method, as the name implies, is the pressure to tap into the atmospheric pressure CVD reactor of a deposition, the deposition rate of this method is very fast (high deposition rate),approximately 600-1000 nm / min. Close to atmospheric pressure(1 atm) the APCVD the

25、operating pressure, the pressure of molecular collisions between the high frequency of homogeneous nucleation gas phase reactions likely to occur, and easy to produce particles (easily generate particles). APCVD use in industrial applications are concentrated in the larger particle endure the proces

26、s, such as the protection layer (just for to passivation).National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Shower head17National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇18Low-pressure chemical vapor deposition during thin

27、film deposition, the gas pressure inside the reactor lowered to below about 100 torr. A chemical vapor deposition reaction. Reaction at low pressure, the film deposited by LPCVD method has better step coverage, but the lower the frequency of collisions between gas molecules makes the LPCVD depositio

28、n rate is slow compared to APCVD.The deposition rate is lower.National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇19National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇In the CVD reaction, the decomposition of gas molecules need

29、 to have sufficient excitation energy .Plasma enhanced chemical vapor deposition method, the reaction gas in an electromagnetic field energy, and a variety of chemical reactions in the plasma body quickly, resulting in a short period of time to complete the chemical vapor deposition.20Belongs to the

30、 non-equilibrium plasma in the PECVD .In the body of such a plasma, the free electrons of the absolute temperature is usually higher than the average gas temperature of 1-2 class times, these high-energy electron impact gas molecules of the reactants, excitation and ionization, resulting in very liv

31、ely chemical properties of free radicals group. Addition , the ions hit the substrate surface, resulting in a more lively surface structure, there by speeding up the chemical reaction. In order to reduce the reaction temperature required to reach the lowered energy consumption for heating, in PECVD

32、share of the weight in the CVD process to gradually become a major thin film deposition tools in Taiwan, especially for IC wafer BEOL metal and dielectric deposition of the plasma membrane.National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Belongs to the non-equi

33、librium plasma in the PECVD. In the body of such a plasma, free electrons of the absolute temperature is usually higher than the average gas temperature 1-2 class times，Free Electrons have high temperature (energy). They will bomb the reactants and gases. The gases will be ionized. The ionics will b

34、e active to react with other ionics. These high-energy electron impact reactant gas molecules, so that excitation and ionization, and chemical properties of very lively radicals. Addition, ion bombardment to the substrate surface, The ionics will also bomb on the substrate surface. Sometime it help

35、deposition, but Sometime it is a damage.More lively surface structure, thereby speeding up the chemical reaction. In order to reduce the reaction temperature required to reach the lowered energy consumption for heating, in PECVD share of the weight in the CVD process to gradually become a major thin

36、 film deposition tools in Taiwan, especially for IC wafer BEOL metal and dielectric deposition of the plasma membrane.21National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇13.56 MHz/ 60MHz50-1000WShower head22National Formosa UniversityInstitute of Electro-Optical

37、 and Material Science太陽能工程-太陽能電池篇ProcessAdvantageShortcomingApplicationAPCVDSimple structure of the reactorFast deposition rateLow temperature processStep coverage of the poor particle pollutionLow temperature oxideLPCVDHigh-purityStep coverage excellentCan be deposited on large area chipsHigh-tempe

38、rature processLow deposition rateHigh-temperature oxidePolysiliconTungsten, silicide tungstenPECVDLow temperature processHigh deposition rateStep coverageChemical pollutionParticle pollutionLow-temperature insulatorPassivation layer23National Formosa UniversityInstitute of Electro-Optical and Materi

39、al Science太陽能工程-太陽能電池篇24National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇25National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇26National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇PECVD wa

40、y to the deposition of thin films, generally have a high hydrogen content in the case of Hydrogen amount is very a high, because the Plasma in the H atoms with unsaturated bonds, not when the deposition statement of Si and N to form the Si-H and NHkey results. Since H is easily affected by temperatu

41、re has been released (H will be released at a high temperature), resulting in the instability of the TFT device characteristics.H in plasma will connected with unsaturated Si and N to become Si-H and N-H27National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇After t

42、he g-of SiNx do an H2, Plasma, change the surface structure of g-of SiNx, to fill some of the Dangling Bond, in order to avoid the Channel with -Si Defect trap caused by Cell Mobility lower28National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Thin film deposition

43、methoda-Si and its alloys is the plasma CVD, the heat of CVD, reactive sputtering or optical CVD method, vapor-phase synthesis method to prepare thin films.The use of a-Si solar cell, to the plasma of CVD method prepared, it is the first production method described, followed by optical CVD method, D

44、oping.29National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇As shown the generated SiHx (x 3) response (neutral and ionic).These reactions are diffusion to reach 100 to 300.C substrate, on which a variety of reactions (adsorption, detachment, pulled out, insert an

45、d surface diffusion process), the formation of a-Si film.Materials and gases to stimulate dissociation filmExcitation, DecompositionTransportSurface reactionFilm30National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Effect Passivation Antireflection Abosrbers Conta

46、cts MaterialSiNx:HSiO2 SiO2, TiO2, Si3N4 a-Si:H, Cu, In, Ga, Se, S,CdTe Al, Ag, NiV, Mo, SbTe, ITO, Ti, Pd, ZnO:Al, i-ZnO Equipment and technologyPECVD Sputtering PECVD Sputtering Sputtering PECVD Evaporation Evaporation Sputtering 31National Formosa UniversityInstitute of Electro-Optical and Materi

47、al Science太陽能工程-太陽能電池篇Solar cell classificationApplications of plasma devicesPlasma coating membranes2004 2020 The first generationSilicon typePECVD、Etcher Antireflection film batch coated93% 50% Second-generationFilm-type(Silicon、II-VI、III-V) PECVD、PVD Transparent conductive film, the metal electro

48、de, the silicon thin film7% 42% Third-generationNano, organic, dyePVD、PECVD SiNx/SiOx film、Transparent conductive filmTiO2/Ta2O5、Metal electrodes0% 8% 32National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Chip film, the initial covered on the wafer surface, many g

49、as molecules or other child, such as atoms and ions. These particles may be because the chemical reaction, the solid particles, and then deposited on the wafer surface; or lose part of the kinetic energy through a surface diffusion campaign, the wafer surface adsorbed (absorbed) were deposited. Acco

50、rding to the order of occurrence can be divided into the following five steps (a) crystal growth (b) the grain growth and (c) grain coalescence (d) seam Road to fill the (e) The deposition film growth.33National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇(a) cryst

51、al growth (b) grain growth and (c) grain coalescence (get together) (d) The seam Road to fill the gap (e) The deposition film growth(1) physical adsorption on the wafer surface adatom(2) adatom back to the gas phase by absorption of the solution34National Formosa UniversityInstitute of Electro-Optic

52、al and Material Science太陽能工程-太陽能電池篇island structure： In the deposition, when the atoms or molecules are mutually binding capacity than the substrate strong island structure, such as metal insulator, graphite and other substrates.layer structure ： As the atoms and the substrate bonding is stronger th

53、an the others. The first layer of coverage completed with the second layer of bonding will be weak, such as semiconductor thin film of single crystal growth.Stranski-Krastanov(S.K.) structure ： Do the aforementioned model of an intermediate process, the current study such behavior is not fully under

54、stood, there may be disturbance to the growth of layered structure due to the binding energy.35National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Within the film and the substrate must have the existence of residual stress (thermal expansion coeff.), residual str

55、ess according to their form to distinguish can be divided into two, divided into the two kinds of tensile stress and compressive stress.The film tensile stress of the role, then the film - substrate will show a concaveshapeFilm by the compressive stress of the role, then the film - substrate will sh

56、ow aconvex shape(a) Tensile stress(b) Compressive stress36National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇Its structure for the strip-type electrodes, However, due to the spacing of theelectrode structure is very narrow, and therefore will produce a standing w

57、ave effect, affecting the quality of thin film growth, the left side of the SignalModulator generated waves phase, the elimination of standing wave effect, in order to improve the filmdeposition quality.37National Formosa UniversityInstitute of Electro-Optical and Material Science太陽能工程-太陽能電池篇 a-Si:H film quality related to the experimental parameters:(1) Substrate temperature (2)SiH4/H2 ratio (3)Total gas flow rate (4)RF power density (5)Electrode to substrate distance (6) growth pressure, To increase the growth rate of a-Si:H films , some possible prob