CN103022146A - Oxide semiconductor material and thin film transistor - Google Patents

Oxide semiconductor material and thin film transistor Download PDF

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Publication number
CN103022146A
CN103022146A CN2012105180872A CN201210518087A CN103022146A CN 103022146 A CN103022146 A CN 103022146A CN 2012105180872 A CN2012105180872 A CN 2012105180872A CN 201210518087 A CN201210518087 A CN 201210518087A CN 103022146 A CN103022146 A CN 103022146A
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semiconductor material
zinc oxide
channel layer
fluoride
film transistor
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CN2012105180872A
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兰林锋
肖鹏
王磊
彭俊彪
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention discloses a zinc oxide-based semiconductor material which is composed by mixing fluoride into the zinc oxide-based semiconductor material. The ratio of the molecule number of the fluoride and the total molecule number of metallic oxide in the zinc oxide-based semiconductor material is greater than or equal to 0.001 and less than or equal to 0.15. The invention also discloses a thin film transistor using the above material as channel layer material. The zinc oxide-based semiconductor material of the invention has the advantages of higher electron mobility, good electrical stability (little hysteresis effect), high switch ratio and the like. The thin film transistor used the zinc oxide-based semiconductor material as the channel layer needs no special process to be processed and can adjust threshold voltage of components by adjusting the content of new dopant to make the components in an often-close state, thereby reducing the driving difficulty and overall power consumption and reducing process cost.

Description

A kind of oxide semiconductor material and thin-film transistor
Technical field
The present invention relates to the oxide semiconductor material field, particularly a kind of oxide semiconductor material reaches with the thin-film transistor of this material as channel layer materials.
Background technology
In recent years, especially in ORGANIC ELECTROLUMINESCENCE DISPLAYS (OLED) field, the thin-film transistor of based oxide semiconductor more and more comes into one's own in flat panel display.The material of semiconductor channel layer that is used at present the thin-film transistor of flat panel display mainly is silicon materials, comprises amorphous silicon (a-Si:H), polysilicon, microcrystal silicon etc.Yet amorphous silicon film transistor has photaesthesia, the low (＜1cm of mobility 2/ Vs) and the shortcoming such as poor stability; Although polycrystalline SiTFT has higher mobility, because the impact of crystal boundary causes its electricity lack of homogeneity, and the polysilicon preparation temperature is high, cost is high and be difficult to the large tracts of land crystallization, has limited its application in flat panel display; It is large that microcrystal silicon prepares difficulty, and crystal grain control technology difficulty is high, is not easy to realize large tracts of land scale volume production.The thin-film transistor of based oxide semiconductor has the higher (1～100cm of carrier mobility 2/ Vs), preparation temperature low (＜400 ℃, far below the fusing point of glass), to advantages such as visible transparent, in the TFT of flat panel display substrate field, the development trend that substitutes with the thin-film transistor of traditional silicon technique preparation is arranged.
Oxide semiconductor material mainly comprises zinc oxide (ZnO), indium zinc oxide (IZO) and indium oxide gallium zinc (IGZO) etc.Wherein, the mobility of ZnO is lower, if be prepared into the ZnO film of the more much higher crystalline substance of mobility, then needs higher temperature, but the uniformity of the ZnO film of polycrystalline and less stable (be the patent documentation of WO200030183-A referring to the patent No.); The IZO mobility is higher, but the subthreshold swing based on the thin-film transistor of IZO is large, stability is not enough, and device is in normally open, and (threshold voltage is negative value, be the document of US2005199959-A referring to the patent No.), therefore device must add a negative voltage and it could be turn-offed when work, has increased driving difficulty and overall power.Although the subthreshold swing of IGZO can improve, its stability is still not enough, and main cause is to contain more oxygen room; Can reduce the oxygen room, improve stability although process (such as steam heat treatment, contain oxygen plasma treatment etc.) by some special process, increase so again operation, strengthened process complexity, improved production cost; In addition based on the threshold voltage of the thin-film transistor of IGZO for still for negative value (be the patent documentation of CN1998087A referring to the patent No.), can improve this phenomenon although in film preparation, improve the content of oxygen, can reduce mobility so again.
Summary of the invention
In view of the above problems, the objective of the invention is to propose a kind of new oxide semiconductor material, this semi-conducting material can reduce oxygen room and dangling bonds, raising stability by introduce the fluoride-doped thing in the Zinc oxide-base material; The present invention has also comprised and utilizes this new oxide semiconductor material as the thin-film transistor of channel layer, this thin-film transistor can just can obtain higher stability (hysteresis effect is little) not needing special process to process (such as steam heat treatment, contain oxygen plasma treatment etc.), and can regulate by the content of adjusting new alloy the threshold voltage of device, so that device is in normal off status, reduce driving difficulty and overall power, reduced simultaneously process costs.
The object of the invention is achieved through the following technical solutions:
A kind of new oxide semiconductor material mixes fluoride by the Zinc oxide-base material and forms.
Described Zinc oxide-base material is (MO) x(In 2O 3) y(ZnO) 1-x-y, wherein MO is Ga 2O 3, Al 2O 3, Nd 2O 3, La 2O 3, SnO 2, TiO 2, HfO 2, Ta 2O 5In more than one, 0≤x≤0.4,0.2≤y≤0.8.
Described fluoride is LiF, CsF, AgF, MgF 2, ZnF 2, AlF 3, InF 3, GaF 3, SnF 4, and TiF 4In more than one.
Fluoride satisfies with the molecular number ratio of Zinc oxide-base material: 0.001≤fluoride/(MO+In 2O 3+ ZnO)≤0.15.
A kind of thin-film transistor comprises:
Grid;
Channel layer;
Insulating barrier is between grid and channel layer;
Source electrode and drain electrode are connected to the two ends of channel layer;
The material of described channel layer forms for mixing fluoride by the Zinc oxide-base material.
Described Zinc oxide-base material is (MO) x(In 2O 3) y(ZnO) 1-x-y, wherein MO is Ga 2O 3, Al 2O 3, Nd 2O 3, La 2O 3, SnO 2, TiO 2, HfO 2, Ta 2O 5In more than one, 0≤x≤0.4,0.2≤y≤0.8.
Described fluoride is LiF, CsF, AgF, MgF 2, ZnF 2, AlF 3, InF 3, GaF 3, SnF 4, and TiF 4In more than one.
Fluoride satisfies 0.001≤fluoride/(MO+In with the molecular number ratio of Zinc oxide-base material 2O 3+ ZnO)≤0.15.
Principle of the present invention is as follows:
Owing to usually contain a large amount of oxygen vacancy defects in traditional Zinc oxide-base material (such as ZnO, IZO, IGZO etc.), cause a large amount of excess carrier, so its intrinsic conductivity is higher, the TFT that is channel layer based on this class material is in normally open; In addition, these oxygen vacancy defects also can have influence on the stability of TFT, show hysteresis effect between the TFT transfer characteristic curve of forward scan and reverse scan and the threshold voltage shift phenomenon under the gate voltage stress induction.After the Zinc oxide-base material mixes fluoride, because the fluorine in the fluoride (F) has extremely strong electronegativity (4.0), be higher than 3.5 of oxygen (O), this just means that fluorine ion has the ability of stronger attraction electronics, so that it is not easy to break away from cation and forms the room, can reduce vacancy defect.Simultaneously, fluorine ion can also be filled oxygen vacancy defect, the minimizing dangling bonds that formed, thereby suppresses generation, the raising stability of intrinsic excess carrier.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) Zinc oxide based semiconductor material of the present invention by introduce the fluoride-doped thing in the Zinc oxide-base material, has reduced oxygen room and dangling bonds, has that electron mobility is higher, an electrical stability good (hysteresis effect is little), on-off ratio advantages of higher;
(2) utilize Zinc oxide based semiconductor material of the present invention can just can obtain higher stability (hysteresis effect is little) not needing special process to process (such as steam heat treatment, contain oxygen plasma treatment etc.) as the thin-film transistor of channel layer, and can regulate by the content of adjusting new alloy the threshold voltage of device, so that device is processed normal off status, reduce driving difficulty and overall power, reduced simultaneously process costs.
Description of drawings
Fig. 1 utilizes oxide semiconductor material of the present invention as the schematic cross-section of the bottom gate top contact thin-film transistor of channel layer;
Fig. 2 be utilize oxide semiconductor material of the present invention as the bottom gate of channel layer at the bottom of the transistorized schematic cross-section of contact membrane;
Fig. 3 be utilize oxide semiconductor material of the present invention as the top grid of channel layer at the bottom of the transistorized schematic cross-section of contact membrane;
Fig. 4 utilizes oxide semiconductor material of the present invention as the schematic cross-section of the top grid top contact thin-film transistor of channel layer;
Fig. 5 is the transfer characteristic curve figure of the thin-film transistor in the embodiment of the invention 1;
Fig. 6 is the transfer characteristic curve figure of the thin-film transistor in the embodiment of the invention 2;
Fig. 7 is the transfer characteristic curve figure of the thin-film transistor in the embodiment of the invention 3.
Embodiment
The present invention will be further described below in conjunction with drawings and embodiments, but need to prove, embodiment does not consist of the restriction to the scope of protection of present invention.
Oxide semiconductor material of the present invention is for to mix fluoride in the Zinc oxide-base material.Wherein the Zinc oxide-base material is the transparent oxide semiconductor material (not comprising pure ZnO) that contains ZnO, such as indium zinc oxide (IZO), indium oxide gallium zinc (IGZO) etc.IZO comprises indium (In) and zinc (Zn), and In and Zn are combined with oxygen and are formed respectively indium oxide (In 2O 3) and zinc oxide (ZnO).IGZO comprises indium, gallium (Ga) and zinc, and In, Ga and Zn are combined with oxygen and are formed respectively In 2O 3, gallium oxide (Ga 2O 3) and ZnO.In addition, also can replace Ga with other metal oxide 2O 3, form (MO) x(In 2O 3) y(ZnO) 1-x-y, wherein MO is NiO, MgO, Al 2O 3, Nd 2O 3, La 2O 3, SnO 2, TiO 2, SiO 2, HfO 2, Ta 2O 5In a kind of, 0≤x≤0.4,0.2≤y≤0.8.
Above-mentioned metal oxide is not limited in the situation of complete stoichiometry coupling, can be not equal to 1 such as the ratio (O/Zn) of the O among the ZnO and Zn, but less than 1, correspond to the ZnO that contains the aerobic room.In addition, mutually displacement and share O between the above-mentioned metal.
Fluoride comprises LiF, CsF, AgF, MgF 2, ZnF 2, AlF 3, InF 3, GaF 3, SnF 4, and TiF 4In more than one.
Above-mentioned fluoride is not limited in the situation of complete stoichiometry coupling, can be not equal to 1 such as the ratio (F/Ag) of the F among the AgF and Ag, but be greater than or less than 1, corresponds to the silver fluoride that lacks fluorine or rich fluorine.
In the present invention, the molecule of all non-stoichiometry couplings all is referred to as the molecule of its corresponding stoichiometry coupling, as: ZnO a, wherein no matter whether a equal 1, is referred to as ZnO, and for example: MgF b, wherein no matter whether b equal 2, is referred to as MgF 2
Owing to usually contain a large amount of oxygen vacancy defects in traditional Zinc oxide-base material (such as ZnO, IZO, IGZO etc.), cause a large amount of excess carrier, so its intrinsic conductivity is higher, the TFT that is channel layer based on this class material is in normally open; In addition, these oxygen vacancy defects also can have influence on the stability of TFT, show hysteresis effect between the TFT transfer characteristic curve of forward scan and reverse scan and the threshold voltage shift phenomenon under the gate voltage stress induction.
After the Zinc oxide-base material mixes fluoride, because the fluorine in the fluoride (F) has extremely strong electronegativity (4.0), be higher than 3.5 of oxygen (O), this just means that fluorine ion has the ability of stronger attraction electronics, so that it is not easy to break away from cation and forms the room, can reduce vacancy defect.Simultaneously, fluorine ion can also be filled oxygen vacancy defect, the minimizing dangling bonds that formed, thereby suppresses generation, the raising stability of intrinsic excess carrier.
The amount of the fluoride that mixes is recently weighed by the molecular number of fluoride and Zinc oxide-base material, and its concrete meaning is: the ratio of the molecular number sum of all the components and the molecular number of fluoride in the Zinc oxide-base material.Molecular number such as IGZO is In 2O 3, Ga 2O 3Molecular number sum with ZnO.
Preferably, fluoride compares more than or equal to 0.001 less than or equal to 0.15 with the molecular number of Zinc oxide-base material.
The described oxide semiconductor material of mixing fluoride can be used as the channel layer of thin-film transistor (TFT), and this TFT can be in order to drive LCD or OLED.
Fig. 1 to Fig. 4 has shown contained the above-mentioned oxide semiconductor material of fluoride of mixing as the cross section structure figure of the TFT of channel layer described in the enforcement mode.Shown in Fig. 1 be the bottom gate top contact structure wherein, shown in Fig. 2 is contact structures at the bottom of the bottom gate, and shown in Fig. 3 is contact structures at the bottom of the grid of top, and shown in Fig. 4 is top grid top contact structure.
Now forward Fig. 1 to, the TFT of a bottom gate top contact structure, comprise: substrate 10, grid 11 is positioned on the substrate 10, insulating barrier 12 is positioned on substrate 10 and the grid 11, channel layer 13 covers on insulating barrier 12 surfaces, and source electrode 14a and drain electrode 14b difference partial coverage are at the two ends of the upper surface of channel layer 13, and the space.Can further include etching barrier layer or passivation layer etc.
Now forward Fig. 2 to, the TFT of contact structures at the bottom of bottom gate, comprise: substrate 20, grid 21 is positioned on the substrate 20, insulating barrier 22 is positioned on substrate 20 and the grid 21, source electrode 23a and drain electrode 23b prepare on insulating barrier 22 and the space, and channel layer 24 covers on the surface of the insulating barrier 22 between source electrode 23a and drain electrode 23b and source electrode 23a and the drain electrode 23b.Can further include passivation layer etc.
Now forward Fig. 3 to, the TFT of contact structures at the bottom of top grid, comprise: substrate 30, source electrode 31a and drain electrode 31b prepare on substrate 30 and the space, channel layer 32 covers on the surface of the substrate 30 between source electrode 31a and drain electrode 31b and source electrode 31a and the drain electrode 31b, insulating barrier 33 covers on channel layer 32, source electrode 31a, drain electrode 31b and the substrate 30, and grid 34 covers on the insulating barrier 33.
Now forward Fig. 4 to, the TFT of a top grid top contact structure, comprise: substrate 40, channel layer 41 is on substrate, source electrode 42a and drain electrode 42b difference partial coverage are at the two ends of the upper surface of channel layer 41, and the space, and insulating barrier 43 covers on channel layer 41, source electrode 42a, drain electrode 42b and the substrate 40, grid, 44 cover on the insulating barrier 43.
Substrate 10,20,30 or 40 can be for the oxidized silicon chip in glass, plastics or surface etc. Grid 11,21,34 and 44 is electric conducting material, such as metal, metal alloy or conducting metal oxide etc., can also be two-layer above electric conducting material, such as Mo/Al/Mo etc., thickness is 100 ~ 1000nm. Insulating barrier 12,22,33 or 43 can be electrolyte such as SiO 2, SiN x, Si-O-N, Al 2O 3, Ta 2O 5, Y 2O 3Or HfO 2In one or more layers, thickness is 50 ~ 1000nm.Source electrode 14a, 23a, 31a or 42a and drain electrode 14b, 23b, 31b or 42b are electric conducting material, such as metal, metal alloy or conducting metal oxide etc., can also two-layer above electric conducting material, and such as Mo/Al/Mo etc., thickness is 100 ~ 1000nm.
Channel layer 13,24,32 or 41 preparation method can be the method for cosputtering, also can be the direct method of sputter, and thickness is between 10 ~ 100nm, and is graphical by the method for mask or photoetching.
The method of cosputtering is with fluoride, MO, In 2O 3And the material such as ZnO is prepared into two above targets by arbitrarily combination and is installed in simultaneously sputter on the different target position, comes the ratio of control ratio different materials by the sputtering power of regulating different target position.
Directly the method for sputter is with fluoride, MO, In 2O 3And four kinds of materials of ZnO proportionally prepare at same target and carry out sputter.
Embodiment 1
The TFT of present embodiment adopts the bottom gate top contact structure, as shown in Figure 1.At first making a layer thickness by the method for sputter on glass substrate is the Al film of 300nm, is undertaken graphically obtaining grid 11 by the method for photoetching.The anodised method manufacturing of insulating barrier 12 usefulness, thickness is 200nm.Channel layer 13 is by the method manufacturing of cosputtering.Adopt the method for sputter to make indium oxide layer tin metal oxide (ITO, Indium Tin Oxides) film on channel layer 13, thickness is 500nm, adopts the method for peeling off (lift-off) graphical, obtains simultaneously source electrode 14a and drain electrode 14b.
Channel layer 13 adopts above-mentioned oxide semiconductor material, mixes fluoride by the Zinc oxide-base material and forms, and the chemical formula of used Zinc oxide-base material is: (In 2O 3) 0.33(ZnO) 0.67, i.e. x=0, y=0.33, used fluoride are MgF 2First with MgF 2Make a target, (In 2O 3) 0.33(ZnO) 0.67Make the another one target, again these two targets are installed in respectively that the method by cosputtering prepares semiconductor material thin film on two different target position.Control MgF by the sputtering power of controlling two target position in the sputter procedure 2With (In 2O 3) 0.33(ZnO) 0.67The molecular number ratio, make respectively MgF 2/ (In 2O 3+ ZnO) be five kinds of films of 0.001,0.017,0.067,0.101,0.15, the thickness of these five kinds of films is 40nm.Fig. 5 shows above-mentioned based on different Mg F 2/ (In 2O 3+ ZnO) the transfer characteristic curve of TFT, as can be seen from the figure, along with MgF 2The increasing of incorporation, (threshold voltage is defined as the threshold voltage of TFT here: in the curve of logarithm with respect to grid current of drain current, the value of drain current corresponding grid voltage when just having begun significantly to rise, all " threshold voltages " of mentioning all use this definition in the bright book of this book) increase to+2V from-7V, work as MgF 2/ (In 2O 3+ ZnO)=0.067 o'clock, the threshold voltage of TFT just is 0V, MgF is mixed in this explanation 2Can make the TFT device adjust to " normal closing " state from " often opening " state; Mix MgF 2The off-state current of rear TFT device also obviously reduces, and illustrates and mixes MgF 2Can suppress superfluous intrinsic carrier.In addition, mix MgF 2Rear TFT device subthreshold swing reduces, and illustrates and mixes MgF 2Can reduce the defective in the channel layer, improve stability.
Embodiment 2
The chemical formula of used Zinc oxide-base material is: (Al 2O 3) 04(In 2O 3) 0.2(ZnO) 0.4, used fluoride is AgF, AgF/ (Al 2O 3+ In 2O 3+ ZnO) be 0.025.
AgF, Al with aforementioned proportion 2O 3, In 2O 3Mix with ZnO powder and to make a ceramic target, by the channel layer of spatter film forming as TFT.
The structure of TFT is contact structures at the bottom of the grid of top, as shown in Figure 3.At first at the three-layer thin-film of glass substrate by the method manufacturing Mo/Al/Mo laminated construction of sputter, thickness is respectively 50nm, 200nm and 50nm, is undertaken graphically by the method for photoetching, obtains source electrode 31a and drain electrode 31b.Again to AgF, Al 2O 3, In 2O 3Make the ceramic target sputter with ZnO powder and form film, thickness is 30nm, is undertaken graphically obtaining channel layer 32 by the method for photoetching.Insulating barrier 33 adopts the thick SiO of method deposition one deck 300nm of plasma enhanced chemical vapor deposition (PECVD) 2With the thick Mo of method deposition one deck 300nm of sputter, cross the method for photoetching and carry out graphically obtaining grid 34 at last.Fig. 6 shows the transfer characteristic curve of the TFT of above-mentioned present embodiment, can find out that the threshold voltage of device is 0V, is in " normal closing " state.
Embodiment 3
The chemical formula of used Zinc oxide-base material is: (Nd 2O 3) 0.1(In 2O 3) 0.8(ZnO) 0.1, used fluoride is ZnF 2, ZnF 2/ (Nd 2O 3+ In 2O 3+ ZnO) be 0.04.
ZnF with aforementioned proportion 2, Nd 2O 3, In 2O 3Mix with ZnO powder and to make a ceramic target, by the channel layer of spatter film forming as TFT.
Adopt the bottom gate top contact structure, as shown in Figure 1.At first making a layer thickness by the method for sputter on glass substrate is the Al film of 300nm, is undertaken graphically obtaining grid 11 by the method for photoetching.The anodised method manufacturing of insulating barrier 12 usefulness, thickness is 200nm.Channel layer 13 is by sputter ZnF 2, Nd 2O 3, In 2O 3The method manufacturing of the ceramic target made from ZnO powder, thickness is 30nm.Adopt the method for sputter to make indium oxide layer tin metal oxide (ITO, Indium Tin Oxides) film on channel layer 13, thickness is 500nm, adopts the method for peeling off (lift-off) graphical, obtains simultaneously source electrode 14a and drain electrode 14b.Fig. 7 shows the transfer characteristic curve of the TFT of above-mentioned present embodiment, can find out that the threshold voltage of device is 0V, is in " normal closing " state.
Above-described embodiment is the better execution mode of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (5)

1. an oxide semiconductor material is characterized in that: mix fluoride by the Zinc oxide-base material and form.
2. oxide semiconductor material according to claim 1 is characterized in that: described Zinc oxide-base material is (MO) x(In 2O 3) y(ZnO) 1-x-y, wherein MO is Ga 2O 3, Al 2O 3, Nd 2O 3, La 2O 3, SnO 2, TiO 2, HfO 2, Ta 2O 5In more than one, 0≤x≤0.4,0.2≤y≤0.8.
3. oxide semiconductor material according to claim 1, it is characterized in that: described fluoride is LiF, CsF, AgF, MgF 2, ZnF 2, AlF 3, InF 3, GaF 3, SnF 4, and TiF 4In more than one.
4. oxide semiconductor material according to claim 2 is characterized in that: the molecular number of fluoride and Zinc oxide-base material is than satisfying 0.001≤fluoride/(MO+In 2O 3+ ZnO)≤0.15.
5. thin-film transistor comprises:
Grid;
Channel layer;
Insulating barrier is between grid and channel layer;
Source electrode and drain electrode are connected to the two ends of channel layer;
It is characterized in that: the material of described channel layer is the described oxide semiconductor material of any one in the claim 1 to 4.
CN2012105180872A 2012-12-05 2012-12-05 Oxide semiconductor material and thin film transistor Pending CN103022146A (en)

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CN104078513A (en) * 2014-07-15 2014-10-01 浙江大学 Amorphous oxide semiconductor film and preparation method and application thereof
CN104143575A (en) * 2014-07-25 2014-11-12 京东方科技集团股份有限公司 Thin film transistor, array substrate and display device
CN106169480A (en) * 2015-05-22 2016-11-30 乐金显示有限公司 There is the thin film transistor base plate of high reliability metal oxide semiconductor material
CN114188354A (en) * 2021-12-02 2022-03-15 深圳市华星光电半导体显示技术有限公司 Array substrate, preparation method thereof and display panel

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104078513A (en) * 2014-07-15 2014-10-01 浙江大学 Amorphous oxide semiconductor film and preparation method and application thereof
CN104143575A (en) * 2014-07-25 2014-11-12 京东方科技集团股份有限公司 Thin film transistor, array substrate and display device
CN106169480A (en) * 2015-05-22 2016-11-30 乐金显示有限公司 There is the thin film transistor base plate of high reliability metal oxide semiconductor material
CN114188354A (en) * 2021-12-02 2022-03-15 深圳市华星光电半导体显示技术有限公司 Array substrate, preparation method thereof and display panel
CN114188354B (en) * 2021-12-02 2023-11-28 深圳市华星光电半导体显示技术有限公司 Array substrate, preparation method thereof and display panel

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Application publication date: 20130403