CN100487945C - Improved organic light-emitting device - Google Patents
Improved organic light-emitting device Download PDFInfo
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- CN100487945C CN100487945C CNB2007100199227A CN200710019922A CN100487945C CN 100487945 C CN100487945 C CN 100487945C CN B2007100199227 A CNB2007100199227 A CN B2007100199227A CN 200710019922 A CN200710019922 A CN 200710019922A CN 100487945 C CN100487945 C CN 100487945C
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Abstract
The invention provides an improved structure of organic luminescent device, i.e. layered structure, which disposes seven layers of material on a transparent conductive glass substrate containing indium tin oxide-ITO, wherein the first layer is 4, 4', 4''-tris(N-3-methylphenyl-N-phenyl-amido)-triphenylamine, and the second layer is 2, 9-dimethyl-4, 7-diphenyl-1, 110-phenanthroline, i.e. BCP layer, and the third layer is N, N'-bis(naphthyl-2-yl)-N, N'-diphenyl-bisdiaminobiphenyl benzene, and the fourth layer is tri-(8-hydroxyquinoline)aluminum-Alq3, and the fifth layer is 2, 9-dimethyl-4, 7-diphenyl-1, 110-phenanthroline, i.e. BCP layer, and the sixth layer is tri-(8-hydroxyquinoline)aluminum-Alq3, the seventh layer is Mg-Ag alloy. The ideal thickness of BCP layer is 1 nm, comparing with a standard device which is not provided with BCP layer, the current efficiency and the power efficiency of current improved device are respectively and remarkably improved 47% and 43%.
Description
Technical field
The invention relates to Organic Light Emitting Diode (OLEDs) structural design and optimization, make it can obtain higher efficient and performance, and can be applied to optical information and show and lighting field.
Background technology
Organic Light Emitting Diode also is referred to as organic electroluminescent LED (OLEDs), because of it has the potentiality of broken colour self-luminous flat panel display and illumination
1,2And seemed more important in recent years.Adopt organic multilayer structure and doping techniques can effectively reduce its driving voltage, and can increase device performance-this is very important in actual applications.Because the device of sandwich construction can the balance hole and the injection/transmission of electronics, exciton can be limited in the light-emitting layer (LEL) away from negative electrode, and can also reduce not matching of energy level between organic material and the electrode.For the hole injection barrier of (HTL) that can reduce ITO and hole transmission layer, level and smooth ITO surface just is necessary to deposit one deck hole injection layer (HIL).In structure is ITO)/m-MTDATA/NPB/Alq
3In the normal component of/Mg:Ag, MTDATA is 4,4 ', 4 ' '-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine can be used as HIL, and NPB is that (N '-diphenyl-two benzidines can be used as HTL, Alq for N, N '-two (naphthyl-2-yl)-N
3Be three-(oxine) aluminium, but double as LEL and electric transmission ETL.Hole injection barrier between ITO and m-MTDATA only is 0.1eV, though Mg:Ag (10:1) alloy has the low work function of 3.7eV, at Alq
3And still there is higher electronics injection barrier 0.6eV between the Mg:Ag negative electrode.Like this, the injection in hole is easy to be more a lot of than electronics.Therefore the hole is for how sub in device, and electronics is few son.In addition, the mobility in NPB in hole than electronics at Alq
3 3Want high many, therefore many greatly than the electric current of electron production, just because the imbalance that hole and electronics inject causes device only to have lower luminous efficiency by the electric current that the hole produces.In order to strengthen the injectability of electronics, the inorganic material of positive some insulation of broad research of people, such as, LiF,
4,5MgF
2,
6CaF
2,
7CsF,
8Al
2O
3,
9NaCl,
10And NaSt,
11The injection rate of electronics is subjected to the influence of the thickness of these insulating material.The ideal thickness of these insulation material layers is generally less than 1nm.On anode ITO layer one side or at negative electrode and anode
12,13Both sides make the ultrathin film of these insulation, can increase electronics significantly and inject number, reduce the injection number in hole simultaneously, and so just the injection rate between energy balance electronic and hole obtains higher luminous efficiency.
2,9-dimethyl-4,7-diphenyl-1,110-phenanthroline (BCP) and 4,4 '-two (carbazole-9-yl)-biphenyl (CBP) is at the organophosphor light emitting devices
14-18Or phosphorescence sensor devices
19-20In, be widely used in respectively behind the LEL as the host material among hole blocking layer and the LET.In these triplet luminescent devices, BCP helps to facilitate the formation of exciton and exciton is controlled in the emitting area, therefore can keep higher optical efficiency.Because BCP has higher ionization potential (6.7eV), the energy level (LUMO) of the minimum not occupied orbital of its molecule is 3.2eV
14,15(approach Alq
33.1eV), electronics just can very freely transmit between ETL and LEL like this.CBP can help phosphorescence host material or dopant material to scatter effectively, to avoid concentration quenching (doping content is generally less than 10%), can also carry out energy delivery, exciton is limited in light-emitting zone and obtains longer phosphorescent lifetime
14CBP is as a kind of good host material, and its ionization potential is 6.3eV, and lumo energy is 3.0eV
15,, so electronics also can transmission freely between ETL and LEL.
List of references:
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10S.J.Kang，D.S.Park，S.Y.Kim，C.N.Whang，K.Jeong，and?S.Im，Appl.Phys.Lett.81，2581(2002).
11Y.Q.Zhan，Z.H.Xiong，H.Z.Shi，S.T.Zhang，Z.Xu，G.Y.Zhong，J.He，J.M.Zhao，Z.J.Wang，E.Obbard，H.J.Ding，X.J.Wang，X.M.Ding，W.Huang，and?X.Y.Hou，Appl.Phys.Lett.83，1656?2003.
12B.J.Chen?and?X.W.Sun，Semicond.Sci.Technol.20，801(2005).
13B.J.Chen，S.C.Tan，and?X.W.Sun，Journal?of?the?SID，13，443(2005).
14M.A.Baldo，S.Lamansky，P.E.Burrows，M.E.Thompson，and?S.R.Forrest，Appl.Phys.Lett.75，4(1999).
15C.Adachi，R.Kwong，and?S.R.Forrest，Organic?Electronics，2，37(2001).
16D.F.O’Brien，M.A.Baldo，M.E.Thompson，and?S.R.Forrest，Appl.Phys.Lett.74，442(1999).
17I.Tanaka，Y.Tabata，and?S.Tokito，Jpn.J.Appl.Phys，43，L1601(2004).
18N.Matsusue，S.Ikame，Y.Suzuki，and?H.Naito，Appl.Phys.Lett.85，4046(2004).
19B.W.D’Andrade，M.A.Baldo，C.Adachi，J.Brooks，M.E.Thompson，and?S.R.Forrest，Appl.Phys.Lett.79，1045(2001).
20M.A.Baldo，M.E.Thompson，and?S.R.Forrest，Nature，403，750(2000).
21V.G.Kozlov，V.Bulovic，P.E.Burrows，M.Baldo，V.B.Khalfin，G.Parthasarathy，S.R.Forrest，Y.You，and?M.E.Thompson，J.Appl.Phys.84，4096(1998).
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of improved organic luminescent device, the improved organic luminescent device by in hole transmission layer and electron transfer layer, inserting ultra-thin hole blocking layer simultaneously, make this luminescent device have stronger electronics injectability and hole barrier ability, when electronics and hole to can obtain higher recombination rate the time, device just can obtain higher current efficiency and power conversion efficiency.
Technical scheme: organic light-emitting device structure of the present invention is a layer structure, promptly is provided with tin indium oxide-above the ITO transparent conducting glass substrate on the surface and successively seven layer materials is set, and this seven layer material is respectively:
Ground floor is 4,4 ', 4 ' '-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine, i.e. m-MTDATA, bed thickness is 20-100nm, m-MTDATA is as hole injection/transport layer,
The second layer is 2,9-dimethyl-4,7-diphenyl-1,110-phenanthroline, i.e. BCP layer; The bed thickness scope between 0.5-2nm,
The 3rd layer is N, N '-two (naphthyl-2-yl)-N, and N '-diphenyl-two benzidines, i.e. NPB layer, bed thickness is 20-100nm.
The 4th layer is three-(oxine) aluminium-Alq
3, bed thickness is 20-80nm, as the Alq of luminescent layer
3Can also be launched the organic/polymer luminescent material of red, green, blue by other or the organic material/polymer of multiple adulterate replaces,
Layer 6 is three-(oxine) aluminium-Alq
3, bed thickness is 20-100nm, as the Alq of electron transfer layer
3Can also be replaced by other organic material/polymer with electronic transmission performance,
Layer 7 is magnesium silver alloy-Mg:Ag, and bed thickness is 200-400nm.
Wherein: the material of ground floor also can be the hole mobile material of CuPc or PEDOT/PSS or starlike polyamines or polyaniline or other oxidants that mixed.
The hole mobile material of the oxidant that mixed is FeCl
3, or SbCl
6, or the tincture of iodine or four (fluorine)-four (cyanogen) Bi Carbazole bismethane or three (4-bromination benzene) aluminium or hexa chloro-antimonate.
The BCP layer of the second layer can also be by other 4,4 '-two (carbazole-9-yl)-biphenyl that higher ionization potential arranged and have the minimum not occupied orbital of molecule, and promptly the CBP material replaces.
The BCP layer of layer 5 can also be by other 4,4 '-two (carbazole-9-yl)-biphenyl that higher ionization potential arranged and have the minimum not occupied orbital of molecule, and promptly the CBP material replaces.
The Mg:Ag negative electrode of layer 7 can by the metal of other low work function or alloy replaces.
Described metal is alloy Li or Ca or Mg:In or Mg:Al or Li:Al or LiF/Al or LiF/Ca/Ag or LiF/Mg:Ag/Ag complex.
Beneficial effect: found through experiments, when the BCP layer thickness is the device of 1nm, current efficiency that it is the highest and energy efficiency are respectively 3.64cd/A and 0.93lm/W, will improve 47% and 43% than the normal component that does not contain the BCP layer respectively.When the BCP bed thickness increased to 2nm, current efficiency and energy efficiency were then reduced to 3.12cd/A and 0.741m/W, and be low by 14% and 20% when being 1nm than BCP bed thickness, but than normal component height (2.47cd/A and 0.65lm/W).In transmission course, how sub the hole is, electronics is few son, and the quantity of hole transport is far longer than electronics, and the size of BCP layer thickness is very big to the injection influence in hole, and little to the injection influence of electronics.Therefore when the BCP layer thickness is suitable, can stop the injection of a certain amount of hole, make hole and electronics in luminescent layer, effectively distribute, obtain the highest combined efficiency.Hole-electron pair has obtained the highest combined efficiency in luminescent layer, thereby device obtains the highest luminescent properties.
Description of drawings
Fig. 1 is the structural representation of the organic small molecule material used in this invention.
Fig. 2 is current density-voltage response (a) and brightness-voltage response (b) in the BCP layer of different-thickness.
Fig. 3 is current efficiency-voltage response (a) and the power efficiency-voltage response (b) with device of different-thickness BCP layer.
Fig. 4 is the EL figure with device of different-thickness BCP layer, and illustration wherein is the level structure figure of device, has shown the relative position of HOMO energy level and lumo energy in each layer of organic layer.
Fig. 5 is a layer structure schematic diagram of the present invention.
Embodiment
Improved organic light-emitting device structure of the present invention is a layer structure, promptly contains the thick tin indium oxide of 60nm-above the ITO transparent conducting glass substrate on the surface and successively seven layer materials is set, and this seven layer material is respectively:
Ground floor is 4,4 ', 4 ' ' (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine (m-MTDATA)-three, bed thickness be 20-100nm.m-MTDATA as hole injection/transport layer, this layer energy replaced by other materials, such as CuPc, PEDOT/PSS, starlike polyamines, polyaniline, and the hole mobile material of other oxidants that mixed is (such as .FeCl
3, SbCl6, the tincture of iodine, four (f fluorine)-four (cyanogen) Bi Carbazole bismethane, three (4-bromination benzene) aluminium, hexa chloro-antimonate etc.);
The second layer is 2,9-dimethyl-4,7-diphenyl-1,110-phenanthroline (BCP), the bed thickness scope between 0.5-2nm, and during 1nm, performance the best of device.The BCP layer can be inserted in electron transfer layer and the hole transmission layer simultaneously as hole blocking layer.BCP can also be by other material that higher ionization potential is arranged and have the minimum not occupied orbital of molecule, and such as 4,4 '-two (carbazole-9-yl)-biphenyl (CBP) replace.
The 3rd layer is N, N '-two (naphthyl-2-yl)-N, and N '-diphenyl-two benzidines (NPB), bed thickness is 20nm;
The 4th layer is three-(oxine) aluminium (Alq
3), bed thickness is 40nm, as the Alq of luminescent layer
3Can also be launched the organic/polymer luminescent material of red, green, blue by other or the organic material/polymer of multiple adulterate replaces;
Layer 6 is three-(oxine) aluminium (Alq
3), bed thickness is the Alq of 20-100nm as luminescent layer
3Can also be launched the organic/polymer luminescent material of red, green, blue by other or the organic material/polymer of multiple adulterate replaces.
Layer 7 is that magnesium silver alloy (Mg:Al) bed thickness is 200-400nm, and the Mg:Ag negative electrode can by the metal of other low work function or alloy replaces, such as Li, and Ca, Mg:In, Mg:Al, Li:Al, or LiF/Al, LiF/Ca/Ag, complexs such as LiF/Mg:Ag/Ag.
Fig. 1 is the structure of the organic small molecule material in the research.OLEDs makes on ITO.The ITO bed thickness is approximately 60nm, its resistance be 50 Ω/square metre.Conventional cleaning step comprises ITO is carried out ultrasonic waves for cleaning in acetone, alcohol, deionized water, isopropyl alcohol, is placed at last in the oxygen plasma chamber and shines.After handling in the oxygen plasma cavity, the ITO substrate is placed to and is used for making device in the vacuum chamber.Ten emission sources are housed in this main vacuum chamber, and each is all heated by a tantalum heater, and the sequence of deposition is being controlled in the folding of baffle plate, and the quartz (controlled) oscillator that deposition rate and thickness are made up of a crystal probe and frequency meter is measured.In order to obtain large-area uniform discontinuous interface, cavity has been installed three class baffle plates, for example, except the baffle plate that is used for crucible, between crucible and substrate, also has a big baffle plate, also have a small front apron under each substrate, thickness/speed crystal probe is installed in the middle of the substrate fixer, along with adjustable rotary speed is rotated.In each operation, there are four samples of identical or different structure to be made, organic membrane one stacked one deck is deposited in the ITO substrate.After having deposited organic layer, not needing to change vacuum degree just can the uppermost cathode layer of evaporation.Cavity is when evaporation organic material and metal, and pressure generally is lower than 2 * 10-4Pa.Four devices are except a parameter difference, and other all parameters are not only the same, and (under same evaporate process) in full accord.This has just been avoided the uncertainty of the experiment that brings in different operating and different evaporate process.The EL spectrum of the device of made measures in the PR650 spectrum scanner.When measuring the EL spectrum, optical splitter is received on the programmable Keithley236 voltage-to-current source, can note brightness-current density-voltage (L-I-V) characteristic, UV, visible light absorption spectra (UV-Vis) can record by UV-2501PC and ultraviolet-visible light recording light spectrometer, and fluorescence spectrum PL measures as excitation source with the 320nm wavelength light in having the RF-5301PC fluorescence spectrum meter (250nm-2000nm) of xenon lamp under the room temperature.All measurements are all carried out at normal temperature and pressure.
We have made the BCP layer of different-thickness, are inserted in them between hole injection layer and the transport layer simultaneously and are inserted in the electron transfer layer.The structure of device is: ITO/m-MTDATA (80nm)/BCP (Xnm)/NPB (20nm)/Alq
3(40nm)/BCP (X nm)/Alq
3(60nm)/and Mg:Ag (200nm), i.e. evaporation seven layer materials successively on the ITO slide, ground floor is the thick m-MTDATA of 80nm, the second layer is that (X can get that 0.5nm～2nm), the 3rd layer is the thick NPB of 20nm that is to the thick BCP of Xnm, and the 4th layer is the thick Alq of 40nm
3, layer 5 is that (X can get that 0.5nm～2nm), layer 6 is the thick Alq of 60nm to the thick BCP of Xnm
3. topmost one deck is the thick magnesium silver alloy of 200nm.
As Fig. 2, each device has the BCP layer of different-thickness, and they are inserted between m-MTDATA and these two hole transmission layers of NPB, and the current density voltage (I-V) of each device and brightness-voltage (L-V) characteristic curve are respectively as Fig. 2 (a) with (b).From I-V, can see in the L-V curve, along with the increase of BCP thickness, curve has mobile slightly to the high direction of voltage, but when the BCP layer thickness increased to 2nm, I-V and L-V curve moved more obvious, curve has reduced a lot, and this is that increase by BCP thickness is caused.Fig. 3 is the current efficiency-voltage (a) of device and the characteristic curve of energy efficiency-voltage (b). under identical driving voltage, thickness has electric current and energy efficiency the highest in all devices for the 1nmBCP layer.When the BCP layer thickness is the device of 1nm, current efficiency that it is the highest and energy efficiency are respectively 3.64cd/A and 0.93lm/W, will improve 47% and 43% than the normal component that does not contain the BCP layer respectively.When the BCP bed thickness increased to 2nm, current efficiency and energy efficiency were then reduced to 3.12cd/A and 0.74lm/W, and be low by 14% and 20% when being 1nm than BCP bed thickness, but than normal component height (2.47cd/A and 0.65lm/W).Fig. 4 is the EL figure of device under the different B CP layer thickness, and illustration wherein is the level structure figure of device, has indicated the HOMO energy level of each layer of organic layer and the relative position of lumo energy.In all devices that we discuss, only from Alq
3Emission be not controlled by extraneous driving voltage and current density.
We can see according to top analysis result, and when the BCP layer thickness was 1nm, it just had the highest electric current and power conversion efficiency.We can see that also electronics is from Alq illustration from Fig. 4
3Layer has the potential barrier of 0.7ev during to the transition of NPB layer, so electronics can effectively be stopped and makes it to be bound in Alq
3In.Electron concentration should be at Alq
3Satisfy certain spatial gradient in the emission layer and distribute, make its maximum concentration appear at NBP layer and Alq
3Layer at the interface, by introducing the BCP organic layer, m-MTDATA hole injection/transport layer and BCP layer at the interface and Alq
3There are the potential barrier of 1.6eV and 0.9eV respectively in luminescent layer and place, BCP bed boundary.The hole is at first stopped at the m-MTDATA layer, secondly at Alq
3Layer is stopped that the hole is the highest in concentration at the interface, is attenuation type then and distributes.When the BCP bed thickness is 0.5nm, cavity energy scatter easily or reaches Alq then by the NBP layer easily
3In the luminescent layer, the minimizing of hole current is stopping owing to the BCP layer then.Because Alq
3The potential barrier that has 0.9eV at the interface of layer and BCP layer is injected Alq
3The hole of layer has effectively been held onto in another interface, place.Since electronics and hole all are limited in Alq
3In the layer, a large amount of electronics and holes accumulate in Alq
3In the luminescent layer, caused the concentration accumulation between the electron hole like this, obtained electron hole pair and formed exciton, and effectively limited and compound process thereupon.The laminated suitable thickness of BCP can make electronics and hole effectively distribute in luminescent layer, obtains the highest combined efficiency.The thickness of BCP is little to the injection influence of electronics, because its lumo energy and Alq
3Be more or less the same.But the BCP layer is too thick, can cause the gathering of hole in the NPB layer, causes light at Alq
3The place produces the radiation of compound with the NPB bed boundary, thereby sharply reduces the performance of device.
OLEDs makes on ITO.The ITO bed thickness is approximately 60nm, its resistance be 50 Ω/square metre.Conventional cleaning step comprises ITO is carried out ultrasonic waves for cleaning in acetone, alcohol, deionized water, isopropyl alcohol, is placed at last in the oxygen plasma chamber and shines.After handling in the oxygen plasma cavity, the ITO substrate is placed to and is used for making device in the vacuum chamber.Ten emission sources are housed in this main vacuum chamber, and each is all heated by a tantalum heater, and the sequence of deposition is being controlled in the folding of baffle plate, and the quartz (controlled) oscillator that deposition rate and thickness are made up of a crystal probe and frequency meter is measured.In order to obtain large-area uniform discontinuous interface, cavity has been installed three class baffle plates, for example, except the baffle plate that is used for crucible, between crucible and substrate, also has a big baffle plate, also have a small front apron under each substrate, thickness/speed crystal probe is installed in the middle of the substrate fixer, along with adjustable rotary speed is rotated.In each operation, there are four samples of identical or different structure to be made, organic membrane one stacked one deck is deposited in the ITO substrate.After having deposited organic layer, not needing to change vacuum degree just can the uppermost cathode layer of evaporation.Cavity is when evaporation organic material and metal, and pressure generally is lower than 2 * 10-4Pa.Four devices are except a parameter difference, and other all parameters are not only the same, and (under same evaporate process) in full accord.This has just been avoided the uncertainty of the experiment that brings in different operating and different evaporate process.The EL spectrum of the device of made measures in the PR650 spectrum scanner.When measuring the EL spectrum, optical splitter is received on the programmable Keithley236 voltage-to-current source, can note brightness-current density-voltage (L-I-V) characteristic, UV, visible light absorption spectra (UV-Vis) can record by UV-2501PC and ultraviolet-visible light recording light spectrometer, and fluorescence spectrum PL measures as excitation source with the 320nm wavelength light in having the RF-5301PC fluorescence spectrum meter (250nm-2000nm) of xenon lamp under the room temperature.All measurements are all carried out at normal temperature and pressure.
Claims (7)
1. improved organic luminescent device, the structure that it is characterized in that this device is a layer structure, promptly successively seven layer materials is set on the surface is provided with the tin indium oxide transparent conductive glass substrate, this seven layer material is respectively:
Ground floor is 4,4 ', 4 "-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine, i.e. m-MTDATA, bed thickness is 20-100nm, m-MTDATA as the hole inject, transport layer,
The second layer is 2,9-dimethyl-4,7-diphenyl-1,110-phenanthroline, i.e. BCP layer; The bed thickness scope between 0.5-2nm,
The 3rd layer is N, N '-two (naphthyl-2-yl)-N, and N '-diphenyl-two benzidines, i.e. NPB layer, bed thickness is 20-100nm,
The 4th layer is three-(oxine) aluminium, i.e. Alq
3, bed thickness is 20-80nm, as the Alq of luminescent layer
3Can also be launched the organic/polymer luminescent material of red, green, blue by other or the organic material/polymer of multiple adulterate replaces,
Layer 5 is 2,9-dimethyl-4,7-diphenyl-1, the 110-phenanthroline, i.e. BCP layer, the bed thickness scope between 0.5-2nm,
Layer 6 is three-(oxine) aluminium, i.e. Alq
3, bed thickness is 20-100nm, as three of electron transfer layer-(oxine) aluminium, i.e. Alq
3Can also be replaced by other organic material/polymer with electronic transmission performance,
Layer 7 is the magnesium silver alloy, i.e. Mg:Ag, and bed thickness is 200-400nm.
2. a kind of improved organic luminescent device according to claim 1 is characterized in that the material of ground floor also can be the hole mobile material of CuPc, PEDOT/PSS, starlike polyamines, polyaniline or other oxidant that mixed.
3. a kind of improved organic luminescent device according to claim 2 is characterized in that described oxidant is FeCl
3, SbCl
6, the tincture of iodine, four (fluorine)-four (cyanogen) Bi Carbazole bismethane, three (4-bromination benzene) aluminium or hexa chloro-antimonate.
4. a kind of improved organic luminescent device according to claim 1, the BCP layer that it is characterized in that the second layer can also be had higher ionization potential and have 4 of the minimum not occupied orbital of molecule by other, 4 '-two (carbazole-9-yl)-biphenyl, promptly the CBP material replaces.
5. a kind of improved organic luminescent device according to claim 1, the BCP layer that it is characterized in that layer 5 can also be had higher ionization potential and have 4 of the minimum not occupied orbital of molecule by other, 4 '-two (carbazole-9-yl)-biphenyl, promptly the CBP material replaces.
6. a kind of improved organic luminescent device according to claim 1, it is characterized in that layer 7 the Mg:Ag negative electrode can by the metal of other low work function or alloy replaces.
7. a kind of improved organic luminescent device according to claim 6 is characterized in that described metal or alloy is Li, Ca, Mg:In, Mg:Al, Li:Al, LiF/Al, LiF/Ca/Ag or LiF/Mg:Ag/Ag complex.
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