CN109427986A - Metal chalcogenide compound of nonmetal doping and its preparation method and application - Google Patents
Metal chalcogenide compound of nonmetal doping and its preparation method and application Download PDFInfo
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- CN109427986A CN109427986A CN201710778261.XA CN201710778261A CN109427986A CN 109427986 A CN109427986 A CN 109427986A CN 201710778261 A CN201710778261 A CN 201710778261A CN 109427986 A CN109427986 A CN 109427986A
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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Abstract
The present invention provides a kind of metal chalcogenide compound of nonmetal doping, the molecular formula of the metal chalcogenide compound of the nonmetal doping is MXnYm, wherein M is metallic element, and X is S and/or Se, and Y is nonmetalloid, and the value range of n, m meet: 2 < n+m < 3.The metal chalcogenide compound of the nonmetal doping, nonmetalloid is doped in metal chalcogenide compound, improve the work function (workfunction range 4.9-5.2eV) of material, when to make it as QLED hole-injecting material, make that there is suitable level-density parameter between adjacent functional layer such as quantum dot light emitting layer, hole transmission layer and electrode, hole injection barrier ladder, reduce the injection barrier in hole, the ability and efficiency for improving hole injection, to improve device efficiency.
Description
Technical field
The invention belongs to flat-panel display device field more particularly to a kind of metal chalcogenide compounds of nonmetal doping
And its preparation method and application.
Background technique
Due to have many advantages, such as narrow FWHM (peak width at half height), Color tunable and can solution method preparation, quantum dot light emitting two
Pole pipe (QLED) becomes the candidate of next-generation display science and technology.Researcher studies QLED from different angles, wherein including to quantum
The research of point (QDs), hole transmission layer (HTL), electron transfer layer (ETL) and electrode；To the properity and stability of device
Research.And in these researchs, the research of device stability is concerned.At present in QLED device, PEDOT:PSS is as normal
The hole injection layer material seen, hole injection efficiency are preferable.However, being easy since PEDOT:PSS has acid and hygroscopic property
ITO and the different degrees of damage and decaying of device are caused, therefore the stability of device need to be improved.The substitution reported at present
In the material of PEODT:PSS, most commonly used is exactly metal oxide, such as molybdenum oxide, nickel oxide or copper oxide etc..
Wherein, it has been reported that using sulfur family metallic compound and substitutes PEDOT:PSS, such as molybdenum sulfide and copper sulfide.Sulfide
Because of its carrier mobility 200-500cm with higher2·V-1·s-1, it is widely used in photocatalysis, transistor and the sun
In energy battery.But if using metal sulfide as hole functional layer, since most of work function of metal sulfide exists
There are certain potential barrier, meetings for the work function (5.2-5.4eV) of 4.8-4.9eV or so, energy level and currently used empty transport layer
Hinder the transmission in hole.It is therefore desirable to the work functions to metal sulfide to regulate and control, its energy level is allowed more to match.
Summary of the invention
The purpose of the present invention is to provide metal chalcogenide compound of a kind of nonmetal doping and preparation method thereof, purports
When the solution prior art uses metal chalcogenide compound as hole-injecting material, since work function is too low, adjacent function
The problem of cannot forming matched energy level between layer and anode, influence hole transport.
Another object of the present invention is to provide a kind of QLED device, the QLED device, which contains above-mentioned nonmetalloid, to be mixed
Miscellaneous metal chalcogenide compound.
The invention is realized in this way a kind of metal chalcogenide compound of nonmetal doping, the nonmetalloid
The molecular formula of the metal chalcogenide compound of doping is MXnYm, wherein M is metallic element, and X is S and/or Se, and Y is nonmetallic member
Element, and the value range of n, m meet: 2 < n+m < 3.
Correspondingly, a kind of preparation method of the metal chalcogenide compound of nonmetal doping, with metal sulfide and/or
Metal selenide adulterates non-gold as target, using magnetically controlled sputter method in the metal sulfide and/or metal selenide
Belong to element, prepares the metal chalcogenide compound of nonmetal doping.
And a kind of QLED device, including anode, hole injection layer, quantum dot light emitting layer and the cathode set gradually, and
Metal chalcogenide compound or the hole injection layer in the hole injection layer containing above-mentioned nonmetal doping is by upper
The preparation method of the metal chalcogenide compound for the nonmetal doping stated prepares.
The metal chalcogenide compound of nonmetal doping provided by the invention is doped with non-in metal chalcogenide compound
Metallic element, improves the work function (workfunction range 4.9-5.2eV) of material, so that it be made to inject material as the hole QLED
When material, make that there is suitable level-density parameter, hole between adjacent functional layer such as quantum dot light emitting layer, hole transmission layer and electrode
Injection barrier ladder reduces the injection barrier in hole, improves the ability and efficiency of hole injection, to improve device effect
Rate.The work function of the metal chalcogenide compound of the nonmetal doping can be carried out according to the doping ratio of nonmetalloid
It adjusts, it, can flexible choice for different electrodes, quantum dot light emitting layer, hole transmission layer.In addition, the nonmetalloid is mixed
Miscellaneous metal chalcogenide compound stability is preferable.
The preparation method of the metal chalcogenide compound of nonmetal doping provided by the invention, using magnetically controlled sputter method
Nonmetalloid is adulterated in the metal sulfide and/or metal selenide, not only deposition rate is fast, depositing temperature is low, at
Film quality is high, controllability is good, and the work function of metal chalcogenide compound and the uniformity of nonmetal doping can be improved,
The metal chalcogenide compound work function of obtained nonmetal doping is higher, can be used for QLED devices field.
QLED device of the present invention contains the metal chalcogenide compound of above-mentioned nonmetal doping in hole injection layer, by
It is higher in the work function of the metal chalcogenide compound of the nonmetal doping, make adjacent functional layer such as quantum dot light emitting
There is suitable level-density parameter, hole injection barrier ladder reduces the injection in hole between layer, hole transmission layer and electrode
Potential barrier improves the ability and efficiency of hole injection, to improve device efficiency.The metal chalcogenide of the nonmetal doping
The work function of compound can be adjusted according to the doping ratio of nonmetalloid, for different electrodes, quantum dot light emitting
Layer, hole transmission layer, can flexible choice.In addition, the metal chalcogenide compound stability of the nonmetal doping is preferable, it can
To improve the stability of device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the QLED device that the embodiment of the present invention 12 provides；
Fig. 2 is the structural schematic diagram for the QLED device that the embodiment of the present invention 16 provides；
Fig. 3 is the structural schematic diagram for the QLED device that the embodiment of the present invention 23 provides；
Fig. 4 is the structural schematic diagram for the QLED device that the embodiment of the present invention 26 provides.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The embodiment of the invention provides a kind of metal chalcogenide compound of nonmetal doping, the nonmetalloid is mixed
The molecular formula of miscellaneous metal chalcogenide compound is MXnYm, wherein M is metallic element, and X is S and/or Se, and Y is nonmetalloid,
And the value range of n, m meet: 2 < n+m < 3.
The metal chalcogenide compound of nonmetal doping provided in an embodiment of the present invention, mixes in metal chalcogenide compound
Miscellaneous nonmetalloid, improves the work function (workfunction range 4.9-5.2eV) of material, to make it as the hole QLED
When injection material, make that there is suitable energy level between adjacent functional layer such as quantum dot light emitting layer, hole transmission layer and electrode
Match, hole injection barrier ladder reduces the injection barrier in hole, the ability and efficiency of hole injection is improved, to mention
High device efficiency.The work function of the metal chalcogenide compound of the nonmetal doping can be according to the doping of nonmetalloid
Ratio is adjusted, can flexible choice for different electrodes, quantum dot light emitting layer, hole transmission layer.In addition, the non-gold
The metal chalcogenide compound stability for belonging to element doping is preferable.
Specifically, molecular formula MXnYmIn, the M is metallic element, and preferably transition metal, transient metal sulfide has
Higher carrier mobility can be used as hole-injecting material use.Specifically, the M can be in Mo, W, V, Nb, Ta
At least one, but not limited to this.
Molecular formula MXnYmIn, 2 < n+m < 3, it is meant that metallic element should meet centainly in the content of the chalcogenide of doping
Requirement, to guarantee the carrier mobility characteristic and conductive characteristic of metal chalcogenide compound.Preferably, the MXnYmIn,
The range of m/n (ratio of m, n) is 0.05-0.3, i.e. the doping ratio of nonmetalloid should meet certain requirement.If institute
The doping ratio for stating nonmetalloid is too low, and the work function of chalcogenide changes less, and the hole as QLED device is injected
When material, the injection barrier in hole cannot be effectively reduced；If the doping ratio of the nonmetalloid is excessively high, metal sulphur can be changed
The property of compounds of group itself, the hole-injecting material for being not suitable as QLED device use, even result in and be unable to get doping
Metal chalcogenide compound.
In the embodiment of the present invention, the Y is preferably at least one of F, Cl, O, N, H.Preferred nonmetalloid, no
It can be only effectively improved the work function of the metal chalcogenide compound of doping, furthermore, it is possible to splash as with gaseous form by magnetic control
Shooting method deposition, method is simple and easy to control, and it is uniform to obtain nonmetal doping in metal chalcogenide compound dopant, and forms a film
Quality is high.
The metal chalcogenide compound of nonmetal doping provided in an embodiment of the present invention can be prepared by following methods
It obtains；Certainly, following methods are to prepare a kind of method of the metal chalcogenide compound of the nonmetal doping, described non-
The metal chalcogenide compound of metallic element doping can also be prepared by other methods.
Correspondingly, the embodiment of the invention provides a kind of preparation sides of the metal chalcogenide compound of nonmetal doping
Method, using metal sulfide and/or metal selenide as target, using magnetically controlled sputter method in the metal sulfide and/or
Nonmetalloid is adulterated in metal selenide, prepares the metal chalcogenide compound of nonmetal doping.
The preparation method of the metal chalcogenide compound of nonmetal doping provided by the invention, using magnetically controlled sputter method
Nonmetalloid is adulterated in the metal sulfide and/or metal selenide, not only deposition rate is fast, depositing temperature is low, at
Film quality is high, controllability is good, and the uniformity of nonmetal doping can be improved, the gold of obtained nonmetal doping
Category chalcogenide work function is higher, stability is good, can be used for QLED devices field.
It is specific preferred, the preparation method of the metal chalcogenide compound of the nonmetal doping, comprising the following steps:
S01. metal sulfide and/or metal selenide are provided as target, to the metal sulfide and/or metallic selenium
Compound carries out pre-sputtering processing；
S02., substrate is provided, the mixed gas of argon gas and doped chemical gas source is passed through, in vacuum degree≤5 × 10-5Pa, function
Magnetron sputtering is carried out under conditions of rate is 100-300w, operating air pressure is 2-5pa, deposits nonmetalloid in the substrate surface
The metal chalcogenide compound film of doping.
Specifically, providing metal sulfide and/or metal selenide as target, directly in target in above-mentioned steps S01
The upper doping that nonmetalloid is carried out by physical method (magnetically controlled sputter method).Specifically exist, before carrying out this magnetron sputtering, first
Pre-sputtering processing is carried out to the metal sulfide and/or metal selenide, to clean target material surface, removes target material surface because of oxygen
The impurity of the formation such as change, pollution.Preferably, the time of the pre-sputtering processing is 10-20min.
In above-mentioned steps S02, substrate is provided, the substrate is the metal chalcogenide compound of nonmetal doping to be deposited
Substrate.When the metal chalcogenide compound of nonmetal doping is used as QLED device, the substrate is hole to be deposited note
Enter the substrate of layer, such as can be also possible to deposit cathode, quantum dot light emitting layer, the even function such as hole transmission layer with anode grid substrate
The substrate of ergosphere.
It is passed through the mixed gas of argon gas and doped chemical gas source, is deposited in the substrate surface by magnetically controlled sputter method
The metal chalcogenide compound film of nonmetal doping.Wherein, the doped chemical gas source refers to the nonmetallic member of doping
The gas source of element.Preferably, the doped chemical gas source is F2、Cl2、O2、N2、H2At least one of.Specifically, the magnetic
Sputter process is controlled in vacuum degree≤5 × 10-5Pa, power 100-300w, operating air pressure carry out under conditions of being 2-5pa, guarantee
Magnetron sputtering is gone on smoothly, and obtains the film of dense uniform.The watt level of the magnetron sputtering processing and processing time are long
The short thickness to film has a certain impact, and when power is too small or the time is too short, is unfavorable for forming complete, fine and close film,
Influence its charge transport properties as hole injection layer when；When power is excessively high or overlong time, the film of formation is blocked up, shadow
It rings light and inhibits the transmission of charge.According to the watt level range, the time of adjustable magnetron sputtering processing, preferably
, the time of the magnetron sputtering is 30-180min.The gas flow of argon gas described in the embodiment of the present invention is 50-70sccm, tool
Body is preferably 60sccm.
In the embodiment of the present invention, it is preferred that the volume ratio of the argon gas and the doped chemical gas source is 9.9:0.1-
9:1.The volume ratio of suitable argon gas, doped chemical gas source is conducive to the doping for controlling doped chemical, obtains work function conjunction
The metal chalcogenide compound of nonmetal doping suitable, stability is strong, can be used as hole-injecting material.
And the embodiment of the invention also provides a kind of QLED device, including set gradually anode, hole injection layer,
Quantum dot light emitting layer and cathode, and contain the metal chalcogenide chemical combination of above-mentioned nonmetal doping in the hole injection layer
Object or the hole injection layer are prepared by the preparation method of the metal chalcogenide compound of above-mentioned nonmetal doping.
QLED device described in the embodiment of the present invention contains the metal chalcogenide of above-mentioned nonmetal doping in hole injection layer
Compound makes adjacent functional layer as measured since the work function of the metal chalcogenide compound of the nonmetal doping is higher
There is suitable level-density parameter between son point luminescent layer, hole transmission layer and electrode, hole injection barrier ladder reduces sky
The injection barrier in cave improves the ability and efficiency of hole injection, to improve device efficiency.The nonmetal doping
The work function of metal chalcogenide compound can be adjusted according to the doping ratio of nonmetalloid, for different electrodes, amount
Son point luminescent layer, hole transmission layer, can flexible choice.In addition, the metal chalcogenide compound of the nonmetal doping is stablized
Property is preferable, and the stability of device can be improved.
As a kind of specific implementation situation, the hole injection layer by nonmetal doping metal chalcogenide compound system
At.When hole injection layer is made of the metal chalcogenide compound of nonmetal doping, the work function of the hole injection layer
Improvement effect becomes apparent from, and is more advantageous between adjacent functional layer (such as hole transmission layer and quantum dot light emitting layer) and anode and is formed
Preferable level-density parameter is conducive to the transmission in hole.
Further, the hole injection layer is made of two layers or two layers or more of function film, and two layers or two layers or more
The function film in, the type of the metal chalcogenide compound of the nonmetal doping is identical or different.For example, described
Hole injection layer includes the metal chalcogenide compound film and Fluorin doped for the hydrogen doping being arranged between anode and hole transmission layer
Metal chalcogenide compound film, the metal chalcogenide compound film of the hydrogen doping and the metal chalcogenide chemical combination of the Fluorin doped
The setting position of object film can be adjusted according to the work function of the two, to form potential barrier ladder, be conducive to hole biography
It is defeated.
In the embodiment of the present invention, in the metal chalcogenide compound of the nonmetal doping, the doping of nonmetalloid
Molar percentage is preferably 5-30%, to form preferable level-density parameter between anode, is conducive to the transmission in hole.Into one
Step is preferred, in two layers or two layers or more of the function film, along the anode to the direction of the quantum dot light emitting layer,
The doping ratio of nonmetalloid gradually increases in the metal chalcogenide compound of nonmetal doping.It is possible thereby to gradually decrease
Energy level potential barrier between adjacent two layers, thereby reduces the potential barrier of hole transport, is conducive to the injection and transmission in hole, Jin Erti
The high efficiency of hole injection, improves the efficiency of device.
As another kind be embodied situation, the hole injection layer by nonmetal doping metal chalcogenide compound
It is made with other hole-injecting materials.In the embodiment of the present invention, other described hole-injecting materials refer to the nonmetalloid
Hole-injecting material other than the metal chalcogenide compound of doping, including but not limited to PEDOT:PSS.By adjusting nonmetallic member
The doping ratio of nonmetalloid in the metal chalcogenide compound of element doping, in hole injection layer nonmetal doping metal
The content of chalcogenide, the work function of adjustable hole injection layer.Further, the hole injection layer is by two layers or two
Layer or more function film constitute, in two layers or two layers or more of the function film, the metal of the nonmetal doping
The type of chalcogenide is identical or different.The setting of two layers or two layers or more of the function film film layer according to work function into
Row adjustment, the hole injection layer of ladder energy level are conducive to transporting holes.
In the embodiment of the present invention, it is preferred that the hole injection layer with a thickness of 10-40nm, to guarantee to have best
While transmission performance, its transparency is in turn ensured.The thickness of the hole injection layer is unsuitable too high or too low, when the hole
When the thickness of implanted layer is too low, will lead to covering it is incomplete, hole inject effect it is poor, even without hole inject effect；When
When the thickness of the hole injection layer is excessively high, the transmission for being unfavorable for charge (when such as film thickness is more than 1um, cannot be used to pass
Transmission of electricity lotus), and will affect the translucency of film, and then influence its use in QLED device.
QLED device described in the embodiment of the present invention includes anode, hole injection layer, quantum dot light emitting layer and cathode, further
It preferably, can also be including at least one layer in hole transmission layer, electron injecting layer, electron transfer layer.It is specific excellent as one
Embodiment is selected, the QLED device includes the anode set gradually, hole injection layer, hole transmission layer, quantum dot light emitting layer, electricity
Sub- implanted layer, electron transfer layer and cathode.
Wherein, the anode includes but is not limited to ITO.
The hole transport layer material can be NiO, CuO, CuS, VOx、WOx、MoOxAt least one of, Huo Zhewei
At least one of TFB, PVK, Poly-TPD, TCTA, CBP, or the combination of above two type, but not limited to this.
The quantum dot light emitting layer can be common red, green, blue and yellow light quantum and infrared and ultraviolet light quantum dot
At least one of.
The electron transfer layer includes but is not limited to N-shaped ZnO, TiO of common positro transmission performance2, low work function
Metals and the ZrO such as Ca, Ba2、CsF、LiF、CsCO3、Alq3Equal electron transport materials.
The cathode can be Ag, Al, Cu, Au and alloy electrode, but not limited to this.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, comprising the following steps:
Glass containing hearth electrode is placed on specimen holder, the preferred ITO of hearth electrode, after vulcanization molybdenum target material is installed,
It is evacuated to 5*10-5For pa hereinafter, then passing to Ar, flow control carries out pre-sputtering in 60sccm, using the power of 100w
20min cleans its surface.Then the power of 200w is used, operating air pressure 3Pa is passed through Ar/Cl2Gaseous mixture,
In, Ar:Cl2=9.5:0.5 sputters 60min, obtains the molybdenum sulfide of Cl doping.
Embodiment 2
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, comprising the following steps:
Glass containing hearth electrode is placed on specimen holder, the preferred ITO of hearth electrode, after vulcanization molybdenum target material is installed,
It is evacuated to 5*10-5For pa hereinafter, then passing to Ar, flow control carries out pre-sputtering in 60sccm, using the power of 100w
20min cleans its surface.Then the power of 200w is used, operating air pressure 3Pa is passed through Ar/Cl2/F2Gaseous mixture,
Wherein, Ar:Cl2: F2=9:0.5:0.5 sputters 60min.Obtain the molybdenum sulfide of F, Cl codope.
Embodiment 3
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, comprising the following steps:
Glass containing hearth electrode is placed on specimen holder, the preferred ITO of hearth electrode, after vulcanization molybdenum target material is installed,
It is evacuated to 5*10-5For pa hereinafter, then passing to Ar, flow control carries out pre-sputtering in 60sccm, using the power of 100w
20min cleans its surface.Then the power of 200w is used, operating air pressure 3Pa is passed through Ar/O2Gaseous mixture,
In, Ar:O2=9.5:0.5 sputters 60min, obtains the molybdenum sulfide of O doping.
Embodiment 4
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, comprising the following steps:
After vulcanization molybdenum target material is installed, it is evacuated to 5*10-5Pa hereinafter, then pass to Ar, flow control in 60sccm,
Pre-sputtering 20min is carried out using the power of 100w, its surface is cleaned.Then the power of 200w is used, operating air pressure is
3Pa is passed through Ar/H2Gaseous mixture, wherein Ar:H2=9.5:0.5 sputters 60min, obtains the molybdenum sulfide of H doping.
Embodiment 5
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, comprising the following steps:
After vulcanization molybdenum target material is installed, it is evacuated to 5*10-5Pa hereinafter, then pass to Ar, flow control in 60sccm,
Pre-sputtering 20min is carried out using the power of 100w, its surface is cleaned.Then the power of 200w is used, operating air pressure is
3Pa is passed through Ar/N2Gaseous mixture, wherein Ar:N2=9.5:0.5 sputters 60min, obtains the molybdenum sulfide of N doping.
Embodiment 6
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, comprising the following steps:
Glass containing hearth electrode is placed on specimen holder, the preferred ITO of hearth electrode, after vulcanization molybdenum target material is installed,
It is evacuated to 5*10-5For pa hereinafter, then passing to Ar, flow control carries out pre-sputtering in 60sccm, using the power of 100w
20min cleans its surface.Then the power of 200w is used, operating air pressure 3Pa is passed through Ar/Cl2Gaseous mixture,
In, Ar:Cl2=9.5:0.5 sputters 30min.The ratio of mixed gas is changed to Ar:Cl2=9:1 sputters 30min, obtains
The MoS of Cl doping with a certain concentration gradientnClm1/MoSnClm2(2 < n+m1 < 3,2 < n+m2 < 3).
Embodiment 7
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, exists with the difference of embodiment 1-6
In target MXnOne of (M=W/V/Nb/Ta, S=S/Se).
Embodiment 8
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, exists with the difference of embodiment 1-6
In target is molybdenum sulfide and selenizing molybdenum.
Embodiment 9
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, exists with the difference of embodiment 1-6
In target is molybdenum sulfide and tungsten selenide.
Embodiment 10
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, exists with the difference of embodiment 1-6
In gaseous mixture Ar/F2/Cl2/O2。
Embodiment 11
A kind of preparation method of the metal chalcogenide compound of nonmetal doping, exists with the difference of embodiment 1-6
In gaseous mixture Ar/N2/O2。
Embodiment 12
A kind of QLED device, as shown in Figure 1, including substrate 1, anode 2, the hole injection layer 3, hole transport set gradually
Layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and cathode 7.
The QLED device the preparation method is as follows:
On the substrate containing hearth electrode (preferred ITO), according to the molybdenum trisulfate of 1 the method for embodiment deposition Cl doping
Film obtains hole injection layer；
Hole transmission layer, quantum dot light emitting layer, electron transfer layer are sequentially depositing on the sulfuric acid molybdenum film of Cl doping；
Top electrode is finally deposited, is finally packaged, QLED device is obtained.
Embodiment 13
A kind of QLED device, with embodiment 12 the difference is that, contain hearth electrode (preferred ITO) substrate
On, according to the vulcanization molybdenum film of 2 the method for embodiment deposition F, Cl codope, obtain hole injection layer.
Embodiment 14
A kind of QLED device, with embodiment 12 the difference is that, contain hearth electrode (preferred ITO) substrate
On, according to the vulcanization molybdenum film of 3 the method for embodiment deposition O doping, obtain hole injection layer.
Embodiment 15
A kind of QLED device, with embodiment 12 the difference is that, contain hearth electrode (preferred ITO) substrate
On, according to the MoS of 6 the method for embodiment deposition Cl dopingnClm1/MoSnClm2Film, wherein 2 < n+m1 < 3,2 < n+m2 < 3,
Obtain hole injection layer.
Embodiment 16
A kind of QLED device, as shown in Fig. 2, including substrate 1, anode 2, the hole injection layer 3, hole transport set gradually
Layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and cathode 7, hole injection layer 3 include that the first hole injection layer 31 and second is empty
Cave implanted layer 32.
The QLED device the preparation method comprises the following steps:
On the substrate containing hearth electrode (such as FTO or being nano-silver thread), one layer is deposited according to 4 the method for embodiment
The vulcanization molybdenum film of H doping, obtains the first hole injection layer；Then according in embodiment 1 on the vulcanization molybdenum film of H doping
Method deposits the vulcanization molybdenum film of Cl doping, obtains the second hole injection layer, the first hole injection layer and the second hole injection layer
Collectively form the hole injection layer of the QLED device；
Hole transmission layer, quantum dot light emitting layer, electron transfer layer are sequentially depositing on hole injection layer；
Top electrode is finally deposited, is finally packaged, QLED device is obtained.
Embodiment 17
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 16
Line) substrate on, according to 4 the method for embodiment deposition H doping vulcanization molybdenum film, obtain the first hole injection layer；Then
According to the vulcanization molybdenum film of method deposition F, Cl codope in embodiment 2 on the vulcanization molybdenum film of H doping, the second sky is obtained
Cave implanted layer, the first hole injection layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 18
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 16
Line) substrate on, according to 4 the method for embodiment deposition H doping vulcanization molybdenum film, obtain the first hole injection layer；Then
According to the vulcanization molybdenum film of the method deposition O codope in embodiment 3 on the vulcanization molybdenum film of H doping, the second hole is obtained
Implanted layer, the first hole injection layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 19
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 16
Line) substrate on, according to 5 the method for embodiment deposition N doping vulcanization molybdenum film, obtain the first hole injection layer；Then
According to the vulcanization molybdenum film of the method deposition Cl doping in embodiment 1 on the vulcanization molybdenum film of N doping, the second hole note is obtained
Enter layer, the first hole injection layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 20
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 16
Line) substrate on, according to 5 the method for embodiment deposition N doping vulcanization molybdenum film, obtain the first hole injection layer；Then
According to the vulcanization molybdenum film of method deposition F, Cl codope in embodiment 2 on the vulcanization molybdenum film of N doping, the second sky is obtained
Cave implanted layer, the first hole injection layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 21
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 16
Line) substrate on, according to 5 the method for embodiment deposition N doping vulcanization molybdenum film, obtain the first hole injection layer；Then
According to the vulcanization molybdenum film of the method deposition O doping in embodiment 3 on the vulcanization molybdenum film of N doping, the second hole note is obtained
Enter layer, the first hole injection layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 22
A kind of QLED device, as shown in figure 3, including the substrate 1 set gradually, cathode 7, electron transfer layer 6, quantum dot hair
Photosphere 5, hole transmission layer 4, hole injection layer 3 and anode 2.
The QLED device the preparation method comprises the following steps:
Electron transfer layer, quantum dot light emitting layer, hole transport are sequentially depositing on the substrate containing hearth electrode (such as ITO)
Layer；
The molybdenum sulfide that deposition Cl is adulterated on the hole transport layer according to the method for embodiment 1；
Top electrode is finally deposited, can be Ag, Al, Cu, Au and alloy electrode, QLED device is obtained after encapsulation.
Embodiment 23
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 23
Line) substrate on, deposit the vulcanization molybdenum film of F, Cl codope on the hole transport layer according to the method for embodiment 2, form institute
State the hole injection layer of QLED device.
Embodiment 24
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 23
Line) substrate on, the vulcanization molybdenum film of O codope is deposited on the hole transport layer according to the method for embodiment 3, described in formation
The hole injection layer of QLED device.
Embodiment 25
A kind of QLED device, the difference is that, containing hearth electrode, (such as FTO is nano silver with embodiment 23
Line) substrate on, according to the method for embodiment 6 deposit on the hole transport layer Cl doping MoSnClm1/MoSnClm2Film,
In, 2 < n+m1 < 3,2 < n+m2 < 3 form the hole injection layer of the QLED device.
Embodiment 26
A kind of QLED device, as shown in figure 4, including the substrate 1 set gradually, cathode 7, electron transfer layer 6, quantum dot hair
Photosphere 5, hole injection layer 3 and anode 1, hole injection layer 3 include the first hole injection layer 31 and the second hole injection layer 32.
The QLED device the preparation method comprises the following steps:
Electron transfer layer, quantum dot light emitting layer are sequentially depositing on the substrate containing hearth electrode (such as ITO)；
According to the vulcanization molybdenum film of 4 the method for embodiment deposition H doping, the first hole injection layer is obtained；Then it is mixed in H
According to the vulcanization molybdenum film of the method deposition Cl doping in embodiment 1 on miscellaneous vulcanization molybdenum film, the second hole injection layer is obtained,
First hole injection layer and the second hole injection layer collectively form the hole injection layer of the QLED device；
Top electrode is finally deposited, can be Ag, Al, Cu, Au and alloy electrode, QLED device is obtained after encapsulation.
Embodiment 27
A kind of QLED device the difference is that, on the substrate containing hearth electrode (such as ITO), is pressed with embodiment 26
According to the vulcanization molybdenum film of 4 the method for embodiment deposition H doping, the first hole injection layer is obtained；Then in the molybdenum sulfide of H doping
According to the vulcanization molybdenum film of method deposition F, Cl codope of embodiment 2 on film, the second hole injection layer, the first hole are obtained
Implanted layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 28
A kind of QLED device the difference is that, on the substrate containing hearth electrode (such as ITO), is pressed with embodiment 26
According to the vulcanization molybdenum film of 4 the method for embodiment deposition H doping, the first hole injection layer is obtained；Then in the molybdenum sulfide of H doping
According to the vulcanization molybdenum film of the method deposition O codope of embodiment 3 on film, the second hole injection layer, the first hole note are obtained
Enter layer and the second hole injection layer collectively forms the hole injection layer of the QLED device.
Embodiment 29
A kind of QLED device the difference is that, on the substrate containing hearth electrode (such as ITO), is pressed with embodiment 26
According to the vulcanization molybdenum film of 5 the method for embodiment deposition N doping, the first hole injection layer is obtained；Then in the molybdenum sulfide of N doping
According to the MoS of the method deposition Cl doping of embodiment 6 on filmnClm1/MoSnClm2Film, wherein 2 < n+m1 < 3,2 < n+m2 <
3, the second hole injection layer is obtained, the first hole injection layer and the second hole injection layer collectively form the hole of the QLED device
Implanted layer.
Embodiment 30
A kind of QLED device the difference is that, on the substrate containing hearth electrode (such as ITO), is pressed with embodiment 26
According to the vulcanization molybdenum film of 5 the method for embodiment deposition N doping, the first hole injection layer is obtained；Then in the molybdenum sulfide of N doping
The vulcanization molybdenum film for depositing Cl doping on film according to the method for embodiment 1 obtains the second hole injection layer, the injection of the first hole
Layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 31
A kind of QLED device the difference is that, on the substrate containing hearth electrode (such as ITO), is pressed with embodiment 26
According to the vulcanization molybdenum film of 5 the method for embodiment deposition N doping, the first hole injection layer is obtained；Then in the molybdenum sulfide of N doping
According to the vulcanization molybdenum film of method deposition F, Cl codope of embodiment 2 on film, the second hole injection layer, the first hole are obtained
Implanted layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 32
A kind of QLED device the difference is that, on the substrate containing hearth electrode (such as ITO), is pressed with embodiment 26
According to the vulcanization molybdenum film of 5 the method for embodiment deposition N doping, the first hole injection layer is obtained；Then in the molybdenum sulfide of N doping
According to the vulcanization molybdenum film of the method deposition O doping of embodiment 3 on film, the second hole injection layer, the injection of the first hole are obtained
Layer and the second hole injection layer collectively form the hole injection layer of the QLED device.
Embodiment 33
A kind of QLED device the difference is that, on the substrate containing hearth electrode (such as ITO), is pressed with embodiment 26
According to the vulcanization molybdenum film of 5 the method for embodiment deposition N doping, the first hole injection layer is obtained；Then in the molybdenum sulfide of N doping
According to the MoS of the method deposition Cl doping of embodiment 6 on filmnClm1/MoSnClm2Film, wherein 2 < n+m1 < 3,2 < n+m2 <
3, the second hole injection layer is obtained, the first hole injection layer and the second hole injection layer collectively form the hole of the QLED device
Implanted layer.
Embodiment 34
A kind of QLED device, including substrate, anode, hole injection layer, quantum dot light emitting layer and the cathode set gradually.
The QLED device the preparation method is as follows:
On the substrate containing hearth electrode (preferred ITO), according to the molybdenum trisulfate of 3 the method for embodiment deposition oxygen doping
Film obtains hole injection layer；
Quantum dot light emitting layer is prepared on the sulfuric acid molybdenum film of oxygen doping；
The evaporating Al electrode on quantum dot light emitting layer, is then packaged, and obtains QLED device.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (14)
1. a kind of metal chalcogenide compound of nonmetal doping, which is characterized in that the metal of the nonmetal doping
The molecular formula of chalcogenide is MXnYm, wherein M is metallic element, and X is S and/or Se, Y is nonmetalloid, and n, m take
It is worth range to meet: 2 < n+m < 3.
2. the metal chalcogenide compound of nonmetal doping as described in claim 1, which is characterized in that the MXnYmIn,
The range of m/n is 0.05-0.3.
3. the metal chalcogenide compound of nonmetal doping as described in claim 1, which is characterized in that the Y be F, Cl,
O, at least one of N, H.
4. the metal chalcogenide compound of nonmetal doping as described in any one of claims 1-3, which is characterized in that described
M is at least one of Mo, W, V, Nb, Ta.
5. a kind of preparation method of the metal chalcogenide compound of nonmetal doping, which is characterized in that with metal sulfide and/
Or metal selenide is adulterated in the metal sulfide and/or metal selenide non-as target using magnetically controlled sputter method
Metallic element prepares the metal chalcogenide compound of nonmetal doping.
6. the preparation method of the metal chalcogenide compound of nonmetal doping as claimed in claim 5, which is characterized in that packet
Include following steps:
Metal sulfide and/or metal selenide are provided as target, the metal sulfide and/or metal selenide are carried out
Pre-sputtering processing；
Substrate is provided, the mixed gas of argon gas and doped chemical gas source is passed through, in vacuum degree≤5 × 10-5Pa, power 100-
300w, operating air pressure carry out magnetron sputtering under conditions of being 2-5pa, in the gold of substrate surface deposition nonmetal doping
Belong to chalcogenide film.
7. the preparation method of the metal chalcogenide compound of nonmetal doping as claimed in claim 6, which is characterized in that institute
Stating doped chemical gas source is F2、Cl2、O2、N2、H2At least one of；And/or
The gas flow of the argon gas is 50-70sccm；And/or
The time of the magnetron sputtering is 30-180min.
8. the preparation method of the metal chalcogenide compound of nonmetal doping as claimed in claims 6 or 7, feature exist
In the volume ratio of the argon gas and the doped chemical gas source is 9.9:0.1-9:1.
9. a kind of QLED device, which is characterized in that including anode, hole injection layer, quantum dot light emitting layer and the yin set gradually
Pole, and the metal chalcogenide chemical combination containing the nonmetal doping as described in claim 1-4 is any in the hole injection layer
Object or the hole injection layer are by the metal chalcogenide chemical combination containing the nonmetal doping as described in claim 5-8 is any
The preparation method of object prepares.
10. QLED device as claimed in claim 9, which is characterized in that the hole injection layer is by nonmetal doping
Metal chalcogenide compound is made；Or
The hole injection layer is made of the metal chalcogenide compound and other hole-injecting materials of nonmetal doping.
11. QLED device as claimed in claim 10, which is characterized in that the hole injection layer is by two layers or two layers or more
Function film constitute, the function film be made of the metal chalcogenide compound of nonmetal doping or the function film by
The metal chalcogenide compound of nonmetal doping and other hole-injecting materials are made, and two layers or two layers or more of the function
In energy film, the type of the metal chalcogenide compound of the nonmetal doping is identical or different.
12. QLED device as claimed in claim 11, which is characterized in that the metal chalcogenide chemical combination of the nonmetal doping
In object, the doping molar percentage of nonmetalloid is 5-30%.
13. QLED device as claimed in claim 12, which is characterized in that in two layers or two layers or more of the function film,
Along the anode to the direction of the quantum dot light emitting layer, nonmetallic member in the metal chalcogenide compound of nonmetal doping
The doping ratio of element gradually increases.
14. such as the described in any item QLED devices of claim 9-13, which is characterized in that the hole injection layer with a thickness of
10-40nm。
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