CN102723438A - An organic resistance random access memory unit, an organic resistance random access memory and a preparation method thereof - Google Patents
An organic resistance random access memory unit, an organic resistance random access memory and a preparation method thereof Download PDFInfo
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- CN102723438A CN102723438A CN2011100767310A CN201110076731A CN102723438A CN 102723438 A CN102723438 A CN 102723438A CN 2011100767310 A CN2011100767310 A CN 2011100767310A CN 201110076731 A CN201110076731 A CN 201110076731A CN 102723438 A CN102723438 A CN 102723438A
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Abstract
The invention discloses an organic resistance random access memory unit, an organic resistance random access memory and a preparation method thereof. The organic resistance random access memory unit, has an anode made of high-work-function metal or electrically conductive polymer and a cathode made of low-work-function metal. An Ohmic contact is formed between the anode and an organic semiconductor layer while a Schottky contact is formed between the cathode and the organic semiconductor layer, and therefore the organic resistance random access memory unit possesses a self-rectifying property. The organic resistance random access memory unit, the organic resistance random access memory and the preparation method thereof solve a problem of misreading of the organic resistance random access memory unit without obviously increasing cost and process complexity.
Description
Technical field
The present invention relates to microelectronic industry memory technology field, relate in particular to a kind of organic resistive random access type memory cell, memory and preparation method thereof.
Background technology
Along with deepening continuously of information technology, electronic product has got into each link of people's life and work.People are increasing to the demand of low cost, flexibility, low weight, portable electronic product in daily life.Traditional device and circuit based on inorganic semiconductor material are difficult to satisfy these requirements.Therefore, the organic integration circuit engineering based on semi-conducting materials such as organic polymer, organic molecules that can realize these characteristics has obtained the many concerns of People more and more under this trend.Organic resistive random access type memory is with a wide range of applications in the organic electronic field.
Organic resistive random access type memory generally has symmetric storage characteristics, in crossed array is integrated, can produce misread phenomenon.In order to address this is that, generally be employed in organic resistive random access type memory wherein the method for an end series diode eliminate misread phenomenon.In realizing process of the present invention, the applicant recognizes that there is following technical problem in prior art: eliminate organic resistive random access type memory through series diode and improved cost and process complexity.
Summary of the invention
The technical problem that (one) will solve
To the above-mentioned technical problem that exists in the prior art; The invention discloses a kind of organic resistive random access type memory cell, memory and preparation method thereof; With under the not obvious prerequisite that raises the cost with process complexity, eliminate the misread phenomenon of organic resistive random access type memory cell.
(2) technical scheme
According to an aspect of the present invention, a kind of organic resistive random access type memory cell is provided.This organic resistive random access type memory cell comprises: dielectric substrate; Be formed at the anode layer on the dielectric substrate, this anode layer is made up of high work function material; Be formed at the organic resistive random access functional layer on the anode layer; And being formed at the cathode layer on the resistance change functional layer, this cathode layer is made up of low-work-function material.
Preferably, in the organic resistive random access type memory cell of the present invention, high work function material is metal, organic complex or the organic conductor of high work function, and wherein: the metal of high work function is: Au or Pt; The organic complex of high work function is: four cyano quino bismethane copper Cu-TCNQ or four cyano quino bismethane silver Ag-TCNQ; The organic conductor of high work function is: 3, and 4-ethene dioxythiophene/polystyrolsulfon acid PEDOT:PSS.
Preferably, in the organic resistive random access type memory cell of the present invention, for anode layer: its thickness is between between the 20nm to 100nm; Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method, ink-jet printing process or spin-coating method.
Preferably, in the organic resistive random access type memory cell of the present invention, low-work-function material is the metal of low work function, and the metal of low work function is: Ca, Mg or Al.
Preferably, in the organic resistive random access type memory cell of the present invention, for cathode layer, its thickness is between between the 20nm to 100nm; Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method or ink-jet printing process.
Preferably, in the organic resistive random access type memory cell of the present invention, the organic resistive random access functional layer comprises: first p type semiconductor layer and second p type semiconductor layer that are positioned at both sides; Nanocrystalline doped layer between first p type semiconductor layer and second p type semiconductor layer; Wherein, The material of first p type semiconductor layer and second p type semiconductor layer is a kind of of following material: pentacene; CuPc or TiOPc, its thickness be all between between the 5nm to 100nm, and its preparation method is a kind of in the following method: vacuum thermal evaporation method or spin-coating method; The material of nanocrystalline doped layer is a kind of of following material: Au, Ag, Al, Al
2O
3, ZrO
2, MoO
3Or SiO
2, its thickness is between between the 2nm to 20nm, and its preparation method is a kind of in the following method: vacuum thermal evaporation method, electron beam evaporation plating method or self-assembly method.
According to another aspect of the present invention, a kind of organic resistive random access type memory also is provided.This organic resistive random access type memory comprises: read-write cell, address selection unit and several above-mentioned organic resistive random access type memory cell; Wherein: address selection unit, link to each other with several organic resistive random access type memory cell, be used to select the organic resistive random access type memory cell of operating; Read-write cell links to each other with several organic resistive random access type memory cell with address selection unit, is used for selected ferroelectric type memory cell is carried out set, resetted or programming operation.
According to a further aspect of the invention, a kind of method for preparing organic resistive random access type memory cell is provided also, has been used to prepare said memory cells.This method comprises: on dielectric substrate, form anode layer, this anode layer is made up of high work function material; On anode layer, form the organic resistive random access functional layer; And on semiconductor layer, forming cathode layer, this cathode layer is made up of low-work-function material.
(3) beneficial effect
Organic resistive random access type memory cell of the present invention, adopting the metal or the conducting polymer of high work function is anode, the metal of low work function is a negative electrode.Form ohmic contact between anode and the organic semiconductor layer, and form Schottky contacts between negative electrode and the organic semiconductor layer, thereby make this organic resistive random access type memory cell have the self-rectifying performance.The present invention has eliminated the misread phenomenon of organic resistive random access type memory cell under the not obvious prerequisite that raises the cost with process complexity.
Description of drawings
Fig. 1 is the structural representation of embodiment of the invention organic resistive random access type memory cell;
Fig. 2 prepares the flow chart of organic resistive random access type memory cell method for the embodiment of the invention;
Fig. 3-1 carries out the structural representation of preceding optical storage unit for flow chart step S10 shown in Figure 2;
Fig. 3-2 is the structural representation of optical storage unit after flow chart step S10 shown in Figure 2 accomplishes;
Fig. 3-3 is the structural representation of optical storage unit after flow chart step S20 shown in Figure 2 accomplishes;
Fig. 3-4 is the structural representation of optical storage unit after flow chart step S30 shown in Figure 2 accomplishes;
Fig. 3-5 is the structural representation of optical storage unit after flow chart step S40 shown in Figure 2 accomplishes;
Fig. 3-6 is the structural representation of optical storage unit after flow chart step S50 shown in Figure 2 accomplishes.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention.
In a basic embodiment of the present invention, a kind of organic resistive random access type memory cell is provided.This organic resistive random access type memory cell comprises: dielectric substrate; Be formed at the anode layer on the dielectric substrate, this anode layer is made up of high work function material; Be formed at the organic resistive random access functional layer on the anode layer; And being formed at the cathode layer on the resistance change functional layer, this cathode layer is made up of low-work-function material.
In the organic resistive random access type memory cell of present embodiment, adopting the metal or the conducting polymer of high work function is anode, and the metal of low work function is a negative electrode.Therefore, anode and organic resistive random access functional layer form ohmic contact, and form Schottky contacts between negative electrode and the organic resistive random access functional layer; Under the memory device initial condition, the charge carrier that injects from anode can be stored in the organic resistive random access functional layer and arrive not negative electrode, and the electric current of memory device is very little; Be high-impedance state, the charge carrier quantity of in the organic resistive random access functional layer, storing reaches certain numerical value, and device will form the conductive channel from the anode to the negative electrode; Thereby become low resistance state, under the low resistance state state, apply forward voltage at anode; Charge carrier can be injected into negative electrode, and when when negative electrode applies forward voltage, owing to be Schottky contacts between negative electrode and the organic resistive random access functional layer; Charge carrier is difficult to inject anode from negative electrode, shows the characteristic of diode at low resistance state.Therefore device has the rectification storage characteristics.Therefore, the organic resistive random access type memory cell that provides in the present embodiment has rectification characteristic, does not raise the cost and process complexity, has not also reduced integrated level.
In the further embodiment organic resistive random access of the present invention type memory cell, high work function material is metal, organic complex or the organic conductor of high work function.Wherein: the metal of high work function comprises: Au, Pt; The organic complex of high work function comprises: four cyano quino bismethane copper Cu-TCNQ or four cyano quino bismethane silver Ag-TCNQ; The organic conductor of high work function comprises: 3, and 4-ethene dioxythiophene/polystyrolsulfon acid PEDOT:PSS.For anode layer: its thickness is between between the 20nm to 100nm; Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method, ink-jet printing process or spin-coating method.Low-work-function material is the metal of low work function, and the metal of low work function comprises: Ca, Mg, Al.For cathode layer, its thickness is between between the 20nm to 100nm; Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method or ink-jet printing process.
In the preferred embodiment of the invention, the organic resistive random access functional layer comprises: first semiconductor layer and second semiconductor layer that are positioned at both sides; Nanocrystalline doped layer between first semiconductor layer and second semiconductor layer.The material of first semiconductor layer and second semiconductor layer is a kind of of following material: pentacene, CuPc, TiOPc, its thickness be all between between the 5nm to 100nm, and its preparation method is a kind of in the following method: vacuum thermal evaporation method or spin-coating method.The material of nanocrystalline doped layer is a kind of of following material: Au, Ag, Al, Al
2O
3, ZrO
2, MoO
3, SiO
2, its thickness is between between the 2nm to 20nm, and its preparation method is a kind of in the following method: vacuum thermal evaporation method, electron beam evaporation plating method or self-assembly method.
In present embodiment organic resistive random access type memory cell; Under the memory device initial condition, the charge carrier that injects from anode can be stored in nanocrystal layer and arrive not negative electrode, and the electric current of memory device is very little; Be high-impedance state; The charge carrier quantity of in nanocrystal layer, storing reaches certain numerical value, and device will form the conductive channel from the anode to the negative electrode, thereby becomes low resistance state.
In addition, the invention also discloses a kind of organic resistive random access type memory.This organic resistive random access type memory comprises: read-write cell, address selection unit and the organic resistive random access type memory cell on several.Wherein: address selection unit, link to each other with some organic resistive random access type memory cell, be used to select the organic resistive random access type memory cell of operating; Read-write cell links to each other with some organic resistive random access type memory cell with address selection unit, is used for selected ferroelectric type memory cell is carried out set, resetted or programming operation.
In addition, the invention also discloses a kind of method for preparing organic resistive random access type memory cell, be used to prepare said memory cells.This method comprises: on dielectric substrate, form anode layer, this anode layer is made up of high work function material; On anode layer, form the organic resistive random access functional layer; And on semiconductor layer, forming cathode layer, this cathode layer is made up of low-work-function material.
This memory has with the identical beneficial effect of above-mentioned memory cell with the method for preparing memory cell, repeats no more here.Below will be at the foregoing description technical, provide optimum embodiment of the present invention.Need explain that this optimum embodiment only is used to understand the present invention, is not limited to protection scope of the present invention.And the characteristic among the optimum embodiment not having under the situation about indicating especially, all is applicable to memory cell, memory and preparation method simultaneously, and the technical characterictic that in identical or different embodiment, occurs can make up use under not conflicting situation.
Fig. 1 is the structural representation of embodiment of the invention organic resistive random access type memory cell.As shown in Figure 1, this organic resistive random access type memory cell comprises: substrate 101; Anode 102; Organic semiconductor layer 103; Nanocrystalline doped layer 104; Organic semiconductor layer 105; And negative electrode 106.Wherein: substrate 101 is conventional dielectric substrate.Anode 102 comes the metal such as the Au of deposition growing high work function for adopting evaporation technique or magnetically controlled sputter method or inkjet printing methods or spin-coating film method, and Pt etc. or organic complex are films such as Cu-TCNQ, Met-TCNQ or Ag-TCNQ etc. or organic conductor PEDOT:PSS.Organic semiconductor layer 103 is the P type organic semiconductor thin-film with electric resistance changing characteristic of the method deposition growing of employing vacuum thermal evaporation or spin-coating film.The metal of the method deposition growing 1-5nm thickness that nanocrystalline doped layer 104 is employing vacuum thermal evaporation or electron beam evaporation plating such as Au, Ag, Al etc. or metal oxide such as Al
2O
3, ZrO
2, MoO
3, SiO
2Deng forming nanocrystalline or adopt the deposition techniques growth metal or the metallic oxide nanocrystal doped layer of self assembly.Organic semiconductor layer 105 is for adopting the deposition growing method growth phase identical with 101 organic semiconductor thin-film together.Negative electrode 106 is the metallic film that adopts evaporation technique or magnetically controlled sputter method or inkjet technology deposition growing low work function, like Ca, and Mg, metallic films such as Al.
The organic resistive random access type memory cell with rectification characteristic of present embodiment, adopting metal or metallic oxide nanocrystal doped P-type organic semiconductor is the organic resistive random access functional layer, the metal of high work function or conducting polymer are anode; The metal of low work function is a negative electrode, so anode and organic semiconductor layer form ohmic contact and negative electrode is a Schottky contacts, under the memory device initial condition; The charge carrier that injects from anode can be stored in nanocrystal layer and arrive not negative electrode, and the electric current of memory device is very little, is high-impedance state; The charge carrier quantity of in nanocrystal layer, storing reaches certain numerical value, and device will form the conductive channel from the anode to the negative electrode, thereby becomes low resistance state; Under the low resistance state state, apply forward voltage at anode, charge carrier can be injected into negative electrode; And when when negative electrode applies forward voltage; Because between negative electrode and the organic semiconductor layer is Schottky contacts, charge carrier is difficult to inject anode from negative electrode, shows the characteristic of diode at low resistance state.Therefore device has the rectification storage characteristics.
Fig. 2 prepares the flow chart of organic resistive random access type memory cell method for the embodiment of the invention.This preparation method can be used to make organic resistive random access type memory cell shown in Figure 1.Fig. 3 is the structural representation of the organic resistive random access type memory cell of each step correspondence in the flow chart shown in Figure 2.As shown in Figure 2, this preparation method comprises:
Step 10, the Au film that adopts electron-beam vapor deposition method deposition 50nm in the insulated substrate surface shown in Fig. 3-1 is as anode, shown in Fig. 3-2;
Step 20 adopts vacuum thermal evaporation method deposition 50nm pentacene thin film at the Au film surface, shown in Fig. 3-3;
Step 30 adopts the Au film of electron beam evaporation plating method deposition 2nm to form nano dot as nanocrystalline doped layer, shown in Fig. 3-4 on the pentacene thin film surface;
Step 40 adopts vacuum thermal evaporation method deposition 50nm pentacene thin film in the Au nanocrystal surface, shown in Fig. 3-5.
Through said method, prepare the memory cell based on organic field effect tube as shown in Figure 1.Adopt and use the same method, the applicant has also prepared following memory cell:
In the second kind memory cell prepared according to the present invention; The thickness of its Au thin film positive pole layer is 20nm, and at first the thickness of the pentacene layer of deposition is 5nm, and the nanocrystalline thickness of Au is 2nm; The thickness of the pentacene layer of deposition is 5nm subsequently, and the thickness of Al film cathode layer is 20nm.
In the third memory cell prepared according to the present invention; The thickness of its Au thin film positive pole layer is 100nm, and at first the thickness of the pentacene layer of deposition is 50nm, and the nanocrystalline thickness of Au is 5nm; The thickness of the pentacene layer of deposition is 100nm subsequently, and the thickness of Al film cathode layer is 100nm.
Test shows, the performance of these three kinds of memory cell has reached designing requirement fully, compares with the prior art memory, all can realize reducing the technique effect of read false rate, and obviously not raise the cost and process complexity.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an organic resistive random access type memory cell is characterized in that, this organic resistive random access type memory cell comprises:
Dielectric substrate;
Be formed at the anode layer on the said dielectric substrate, this anode layer is made up of high work function material;
Be formed at the organic resistive random access functional layer on the said anode layer; And
Be formed at said resistance and become the cathode layer on the functional layer, this cathode layer is made up of low-work-function material.
2. organic resistive random access type memory cell according to claim 1 is characterized in that, said high work function material is metal, organic complex or the organic conductor of high work function, wherein:
The metal of said high work function is: Au or Pt;
The organic complex of said high work function is: four cyano quino bismethane copper Cu-TCNQ or four cyano quino bismethane silver Ag-TCNQ;
The organic conductor of said high work function is: 3, and 4-ethene dioxythiophene/polystyrolsulfon acid PEDOT:PSS.
3. organic resistive random access type memory cell according to claim 2 is characterized in that, for said anode layer:
Its thickness is between between the 20nm to 100nm;
Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method, ink-jet printing process or spin-coating method.
4. organic resistive random access type memory cell according to claim 1 is characterized in that said low-work-function material is the metal of low work function, and the metal of said low work function is: Ca, Mg or Al.
5. organic resistive random access type memory cell according to claim 1 is characterized in that, for said cathode layer,
Its thickness is between between the 20nm to 100nm;
Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method or ink-jet printing process.
6. organic resistive random access type memory cell according to claim 1 is characterized in that, said organic resistive random access functional layer comprises: first p type semiconductor layer and second p type semiconductor layer that are positioned at both sides; Nanocrystalline doped layer between said first p type semiconductor layer and second p type semiconductor layer, wherein,
The material of said first p type semiconductor layer and second p type semiconductor layer is a kind of of following material: pentacene; CuPc or TiOPc; Its thickness is all between between the 5nm to 100nm, and its preparation method is a kind of in the following method: vacuum thermal evaporation method or spin-coating method;
The material of said nanocrystalline doped layer is a kind of of following material: Au, Ag, Al, Al
2O
3, ZrO
2, MoO
3Or SiO
2, its thickness is between between the 2nm to 20nm, and its preparation method is a kind of in the following method: vacuum thermal evaporation method, electron beam evaporation plating method or self-assembly method.
7. an organic resistive random access type memory is characterized in that, this organic resistive random access type memory comprises: each described organic resistive random access type memory cell in read-write cell, address selection unit and several claims 1 to 6; Wherein:
Said address selection unit links to each other with said several organic resistive random access type memory cell, is used to select the organic resistive random access type memory cell of operating;
Said read-write cell links to each other with said several organic resistive random access type memory cell with said address selection unit, is used for selected ferroelectric type memory cell is carried out set, resetted or programming operation.
8. a method for preparing organic resistive random access type memory cell is used for preparation like each said memory cell of claim 1 to 6, it is characterized in that this method comprises:
On said dielectric substrate, form anode layer, this anode layer is made up of high work function material;
On said anode layer, form the organic resistive random access functional layer; And
On said semiconductor layer, form cathode layer, this cathode layer is made up of low-work-function material.
9. the method for preparing organic resistive random access type memory cell according to claim 8 is characterized in that,
Said high work function material is metal, organic complex or the organic conductor of high work function, and wherein: the metal of said high work function is: Au or Pt; The organic complex of said high work function is: four cyano quino bismethane copper Cu-TCNQ or four cyano quino bismethane silver Ag-TCNQ; The organic conductor of said high work function is: 3, and 4-ethene dioxythiophene/polystyrolsulfon acid PEDOT:PSS; Its thickness is between between the 20nm to 100nm; Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method, ink-jet printing process or spin-coating method.
Said low-work-function material is the metal of low work function, and the metal of said low work function is: Ca, and Mg or Al, its thickness is between between the 20nm to 100nm; Its preparation method is a kind of in the following method: evaporation, magnetron sputtering method or ink-jet printing process.
10. the method for preparing organic resistive random access type memory according to claim 9 is characterized in that:
The said step that on dielectric substrate, forms anode layer comprises: the thick Au film of technology growth 50nm that adopts electron beam evaporation in insulated substrate surface;
The said step that on anode layer, forms semiconductor layer comprises: adopt vacuum thermal evaporation method deposition growing 50nm pentacene thin film on Au anode film surface; Adopt the thick Au film of electron beam evaporation methods growth 2nm to form nano dot as nanocrystalline doped layer on the pentacene surface; Adopt vacuum thermal evaporation method deposition growing 50nm pentacene thin film in the Au nanocrystal surface;
The said step that on semiconductor layer, forms cathode layer comprises: adopt the thick Al of electron-beam vapor deposition method deposition growing 50nm as negative electrode on the pentacene thin film surface.
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Application publication date: 20121010 |