CN102544356B - Method for preparing heating layer of phase change memory - Google Patents
Method for preparing heating layer of phase change memory Download PDFInfo
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- CN102544356B CN102544356B CN 201010594920 CN201010594920A CN102544356B CN 102544356 B CN102544356 B CN 102544356B CN 201010594920 CN201010594920 CN 201010594920 CN 201010594920 A CN201010594920 A CN 201010594920A CN 102544356 B CN102544356 B CN 102544356B
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- phase transition
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Abstract
The invention relates to a method for preparing a heating layer of a phase change memory in the technical field of preparation of semiconductors, which comprises the steps of: forming the heating layer on a lower electrode by the selective extensional method, wherein the reaction gas by the selective extensional method comprises Si atoms and heating particles. Furthermore, the thickness of the heating layer is ranged from 20 angstrom to 5000 angstrom, and the resistivity is ranged from 10 <-5> ohm*cm to 10 <2> ohm*cm. The heating particles comprise one of Ge ions, Ta ions, W ions, Sb ions or C atoms. According to the invention, the selective extensional method is adopted to replace the ion infusion method in the prior art so as to form the heating layer of the phase change memory without further annealing treatment. The heating ions in the heating layer are distributed uniformly, so that the performance of the heating layer is uniform. The thickness of the heating layer and the content of the heating particles are easy to control so as not to damage the function layer below the heating layer.
Description
Technical field
What the present invention relates to is a kind of method of semiconductor fabrication technical field, specifically is a kind of zone of heating preparation method of phase transition storage.
Background technology
Recently, (Phase Change RAM, PCRAM) device (abbreviation phase transition storage) is as non-volatile memory semiconductor device to have proposed the phase-change random access storage.The unit storage unit of phase transition storage uses phase-change material as data storage media.Phase-change material is according to being supplied to its heat to have two kinds of stable phases (for example: amorphous phase and crystalline phase).Known phase-change material has Ge-Sb-Te (GST) compound, and it is the mixture of germanium (Ge), antimony (Sb) and tellurium (Te).Supply heat is to realize the phase transformation in the phase-change material.
If under near the temperature of the melt temperature of phase-change material phase-change material is heated short time and then cooling fast, then phase-change material fades to amorphous phase from crystalline phase.In contrast, if be lower than under the crystallization temperature of melt temperature the phase-change material heating long-time, then slowly cooling, then phase-change material from amorphous phase-change to crystalline phase.Phase-change material under amorphous phase than under crystalline phase, having higher resistivity.Therefore, be stored in data in the phase-change memory cell be logic " 1 (amorphous phase, high resistance) " still logic " 0 (crystalline phase, low resistance) " can judge by the flow through electric current of phase-change material of detection.
Prior art is by inserting zone of heating to improve the thermal effect of device between the bottom electrode of phase transition storage and phase change layer, as shown in Figure 1, phase transition storage comprises:
Zone of heating 103, described zone of heating 103 are positioned on the P-type conduction layer of described bottom electrode 102;
Insulating medium layer 106, described insulating medium layer 106 are positioned at two ends and described insulating medium layer 106 adjacent described zone of heating 103 and the described phase change layers 104 on the described bottom electrode 102.
Described zone of heating 103 should be not undergo phase transition, and has the material of high electrical resistance and the lower coefficient of heat conduction.As: WO
3(tungstic acid), Ta
2O
5(tantalum pentoxide), SrS (strontium sulfide), silicide, Ge (germanium), amorphous carbon material etc.
The structure of phase transition storage is not limited to structure shown in Figure 1 in the prior art, if any phase transition storage in first phase change layer be positioned on the bottom electrode, zone of heating is positioned on first phase change layer, second phase change layer is positioned on the zone of heating.
But mostly prior art for preparing wherein is the method that adopts ion to inject during zone of heating, as: behind bottom electrode 102 as described in the preparation, the Ge ion is injected in the P type semiconductor zone of bottom electrode 102 shown in Figure 1, thereby form the zone of heating 103 that contains Si atom, P type ion (mostly being the boron ion) and Ge ion.
The zone of heating that the method that adopts above-mentioned ion to inject forms phase transition storage has following shortcoming (still injecting the Ge ion with Fig. 1 is example):
1, the mode injected of ion will produce a large amount of lattice defects, and the impurity major part of injecting rests on the interstitial site place, so also need to carry out annealing in process;
Even if 2 annealed processing, the concentration of Ge ion remains pockety in the zone of heating, thereby makes that the performance of zone of heating is inhomogeneous;
3, the degree of depth and the concentration of injecting the Ge ion is difficult for better controlled, so the Ge ion may enter described P-type conduction layer, thereby influences the performance of described bottom electrode 102.
Summary of the invention
The problem that the present invention solves is: the zone of heating preparation method that a kind of phase transition storage is provided, make the zone of heating of preparation to the not influence of performance of functional layer below it, and heating material is evenly distributed in the zone of heating, thickness and the concentration of zone of heating can better be controlled.
For addressing the above problem, the invention provides a kind of zone of heating preparation method of phase transition storage, comprise: form zone of heating at bottom electrode, form zone of heating and adopt the selective epitaxial method, the reacting gas of selection type extension comprises: Si atom and heating particle.
Alternatively, the thickness range of described zone of heating is
Electrical resistivity range is 10
-5～10
2Ω cm's.
Alternatively, described heating comprises with particle: a kind of in Ge ion, Ta ion, W ion, Sb ion or the C atom.
Alternatively, forming described zone of heating also comprises: the reacting gas of described selective epitaxial also comprises the boron ion.
Alternatively, described epitaxy method comprises: any of molecular beam epitaxy (MBE), high vacuum chemical vapour deposition (UHV/CVD) extension, low-pressure chemical vapor deposition (LPCVD) extension and the outer Yanzhong of rpcvd (RPCVD).
Alternatively, described zone of heating is between described bottom electrode and phase change layer, and described phase change layer is positioned on the described zone of heating.
Alternatively, described zone of heating is between first phase change layer and second phase change layer, and described first phase change layer is positioned on the described bottom electrode, and described second phase change layer is positioned on the described zone of heating.
Compared with prior art, advantage of the present invention is: adopt the selective epitaxial method to replace ion injection method of the prior art to form the zone of heating of phase transition storage, need not further to carry out annealing in process; Heating is equally distributed with particle in the zone of heating, thereby the performance of zone of heating also is uniform; The thickness of zone of heating and heating are easy to control with the content of particle, thereby can not damage the functional layer below the zone of heating.
Description of drawings
Fig. 1 is the structural representation of a kind of phase transition storage in the prior art;
Fig. 2 is the schematic flow sheet that the method for employing selectivity RPCVD epitaxial Germanium base silicon prepares the phase transition storage zone of heating;
Fig. 3 is the structural representation of the semi-finished product print of one embodiment of the invention;
Fig. 4 is the structural representation that one embodiment of the invention prepares the semi-finished product print behind the zone of heating;
Fig. 5 is the structural representation of one embodiment of the invention phase transition storage;
Fig. 6 is the structural representation of another embodiment of the present invention phase transition storage.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.
Set forth a lot of details in the following description so that fully understand the present invention, implement but the present invention can also adopt other to be different from alternate manner described here, so the present invention has not been subjected to the restriction of following public specific embodiment.
Just as described in the background section, when prior art contains the phase transition storage of zone of heating in preparation, the method that adopts ion to inject forms the zone of heating of phase transition storage, thereby causes: increase that annealing in process, zone of heating performance are inhomogeneous, the defective of the performance etc. of functional layer below the influence.
Therefore, when manufacturing contains the phase transition storage of zone of heating, for preventing above-mentioned generation of defects, the zone of heating preparation method of phase transition storage provided by the invention, comprise: form zone of heating at bottom electrode, form zone of heating and adopt the selective epitaxial method, the reacting gas of selection type extension comprises: Si atom and heating particle.
Heating among the present invention can be selected Ge ion, Ta ion, W ion, Sb ion or C atom etc. for use with particle, so long as the available technology adopting ion injects or doping way available ion or atom when preparing the zone of heating of phase transition storage, can be as heating particle of the present invention.
The thickness range of the zone of heating that the present invention prepares is
Electrical resistivity range is 10
-5～10
2Ω cm.
Further, forming described zone of heating also comprises: the reacting gas of described selective epitaxial also comprises the boron ion, be that the present invention adopts the selective epitaxial method Si atom of growing simultaneously, heating particle and boron ion, the material content of the zone of heating that obtains like this and prior art are identical with the material content of the zone of heating that the ion injection mode obtains, inject the performance that the zone of heating obtain and the present invention adopt the zone of heating that the selective epitaxial method obtains by analyzing prior art intuitively by ion, can find: the resistance of the zone of heating that the inventive method obtains is higher, and the coefficient of heat conduction is lower, so the performance of the zone of heating that obtains of the inventive method is better.
The present invention adopts the selective epitaxial method to replace ion injection method of the prior art to form the zone of heating of phase transition storage, need not further to carry out annealing in process; Heating is equally distributed with particle in the zone of heating, thereby the performance of zone of heating also is uniform; The thickness of zone of heating and heating are easy to control with the content of particle, thereby can not damage the functional layer below the zone of heating.
The zone of heating for preparing in the phase transition storage with the method that adopts rpcvd (RPCVD) selective epitaxial germanium base silicon is example below, is elaborated.
As shown in Figure 2, the zone of heating preparation method of the phase transition storage that provides of present embodiment may further comprise the steps:
S100 cleans the semi-finished product print, removes the impurity on the described semi-finished product print, obtains clean semi-finished product print;
S110, described clean semi-finished product print is put into the rpcvd reaction cavity, described rpcvd reaction cavity is heated and reduces pressure and simultaneously charge into hydrogen in described rpcvd reaction cavity, make described rpcvd reaction cavity reach first temperature and first pressure;
S120, continuation is heated described rpcvd reaction cavity and is reduced pressure and continue charge into hydrogen in described rpcvd reaction cavity, keep described rpcvd reaction cavity to be in the condition of first temperature and second pressure, and in described rpcvd reaction cavity, charge into hydrogen, silica-based gas, germanium base gas and selective gas simultaneously;
S130, when the thickness of epitaxially grown zone of heating reaches first thickness, stop in described rpcvd reaction cavity, to charge into silica-based gas, germanium base gas and selective gas and stop heating and decompression to described rpcvd reaction cavity simultaneously, make described rpcvd reaction cavity cooling;
S140 takes out the semi-finished product print that comprises zone of heating in described rpcvd reaction cavity, finish the preparation of phase transition storage zone of heating.
Semi-finished product print described in the present invention refers to prepare the semi-finished product of the phase transition storage of zone of heating.Present embodiment is directly to form zone of heating at described bottom electrode, and as shown in Figure 3, the semi-finished product print in the present embodiment comprises:
Insulating medium layer 206, described insulating medium layer 206 is positioned at the two ends in described N+ zone 201;
The bottom electrode 202 of PN diode structure, described bottom electrode 202 is on the N+ zone 201 between the described insulating medium layer 206.
At first execution in step S100 cleans the semi-finished product print, removes the impurity on the described print, obtains clean semi-finished product print.Specifically comprise:
A, be H with the composition ratio
2SO
4: H
2O
2=5: 1 or 4: 1 acid liquid clean, organic substance decomposed and remove;
B, with after the ultra-pure water flushing, be H with the composition ratio again
2O: H
2O
2: NH
4OH=5: the alkaline cleaning fluid of 2: 1 or 5: 1: 1 or 7: 2: 1 cleans, because H
2O
2Oxidation and NH
4The complexing of OH, many metal ions form stable soluble complexes and are water-soluble;
C, use composition than being H then
2O: H
2O
2: HCL=7: the acidic cleaning solution of 2: 1 or 5: 2: 1, because H
2O
2Oxidation and the dissolving of hydrochloric acid, and the complexing of chloride ion, many metals generate water-soluble complex ion, thereby reach the purpose of cleaning.
In other embodiments of the invention, other cleaning methods well-known to those skilled in the art (as RCA cleaning method etc.) can also be adopted, protection scope of the present invention should be do not limited at this.
Follow execution in step S110, described clean semi-finished product print is put into the rpcvd reaction cavity, described rpcvd reaction cavity is heated and reduces pressure and simultaneously charge into hydrogen in described rpcvd reaction cavity, make described rpcvd reaction cavity reach first temperature and first pressure, second pressure is less than first pressure.
The flow of hydrogen is controlled all the time at 0.1slm to 100slm in the present embodiment, and is charging into hydrogen all the time in described rpcvd reaction cavity in step S110, S120 and S130.
The scope of first temperature comprises in the present embodiment: 550 ℃～1100 ℃, the scope of first pressure comprises: 5～700 holders (1 holder=133.32 Pascals), namely when the temperature in the described rpcvd reaction cavity between 550 ℃～900 ℃ and pressure be positioned at for 5～700 whens holder, just can execution in step S120.
Follow execution in step S120, continuation is heated described rpcvd reaction cavity and is reduced pressure and continue charge into hydrogen in described rpcvd reaction cavity, keep described rpcvd reaction cavity to be in the condition of first temperature and second pressure, and in described rpcvd reaction cavity, charge into hydrogen, silica-based gas, germanium base gas and selective gas simultaneously.
The scope of second pressure comprises described in the present embodiment: 1～20 holder.That is: by described rpcvd reaction cavity being heated and reducing pressure, the temperature of described rpcvd reaction cavity is remained between 550 ℃～1100 ℃, pressure remains between 1～20 holder, simultaneously in described rpcvd reaction cavity, charge into hydrogen, silica-based gas, germanium base gas and selective gas, wherein: the effect of silica-based gas provides the Si atom, the effect of germanium base gas provides the Ge ion, the effect of selective gas is to guarantee that silica-based germanium only is grown on the P-type conduction layer, and can not be grown on the insulating medium layer.
Described silica-based gas comprises: SiH
4, SiH
2Cl
2And Si
2H
6In one or more, and the range of flow of silica-based gas comprises: 1sccm to 1000sccm; Described germanium base gas comprises: GeH
4, and the range of flow of described germanium base gas comprises: 1sccm to 1000sccm; Described selective gas comprises: HCl, and the range of flow of described selective gas comprises: 1sccm to 1000sccm.
In another embodiment of the present invention, when in described rpcvd reaction cavity, charging into hydrogen, silica-based gas, germanium base gas and selective gas, also in described rpcvd reaction cavity, charge into boryl gas, in to reative cell, charge into the B that range of flow comprises 1sccm to 1000sccm
2H
6
Follow execution in step S130, when the thickness of epitaxially grown zone of heating reaches first thickness, stop in described rpcvd reaction cavity, to charge into silica-based gas, germanium base gas and selective gas and stop heating and decompression to described rpcvd reaction cavity simultaneously, make described rpcvd reaction cavity cooling.
The span of first thickness comprises in the present embodiment:
Extremely
Namely the thickness when epitaxially grown zone of heating is positioned at
Extremely
Between the time, the zone of heating that phase transition storage is described forms, stop in described rpcvd reaction cavity, to charge into silica-based gas, germanium base gas and selective gas this moment and stop heating and decompression to described rpcvd reaction cavity simultaneously, make described rpcvd reaction cavity cooling.Need to prove, also need this moment to continue in described rpcvd reaction cavity, to charge into hydrogen.
In another embodiment of the present invention, when stopping in described rpcvd reaction cavity, charging into silica-based gas, germanium base gas and selective gas, also need to stop in described rpcvd reaction cavity, to charge into boryl gas.
Last execution in step S140 takes out the semi-finished product print that comprises zone of heating in described rpcvd reaction cavity, finish the preparation of phase transition storage zone of heating.
As shown in Figure 4, when present embodiment is cooled to room temperature when described rpcvd reaction cavity, stop to charge into hydrogen, comprised zone of heating 203 on the semi-finished product print of this moment, the semi-finished product print that comprises zone of heating 203 is taken out in described rpcvd reaction cavity, finish the preparation of phase transition storage zone of heating.As shown in Figure 5, after the preparation of finishing the phase transition storage zone of heating, will adopt prior art to form phase change layer 204 and top electrode 205 etc. at described zone of heating 203, this all is the technology of comparative maturity to one skilled in the art, does not repeat them here.
Need to prove, in other embodiments of the invention, can also select other selective epitaxial growth method for use, as: molecular beam epitaxy, high vacuum chemical vapour deposition extension, low-pressure chemical vapor deposition extension etc.These selective epitaxial growth methods are known for a person skilled in the art, so do not repeat them here.In addition, adopt the inventive method can only not prepare the zone of heating of phase transition storage shown in Figure 5, the scope of application of the inventive method is the zone of heating of all phase transition storages, as when adopting the present invention to prepare the method for phase change layer, forms first phase change layer at described bottom electrode earlier; Form described zone of heating at described first phase change layer again, when described zone of heating formed the second phase change layer top electrode, the phase transition storage that obtains comprised as shown in Figure 6 then:
Insulating medium layer 306, described insulating medium layer 306 is positioned at the two ends in described N+ zone 301;
The bottom electrode 302 of PN diode structure, described bottom electrode 302 is on the N+ zone 301 between the described insulating medium layer 306.
The first phase change layer 304a is positioned on the described bottom electrode 302;
Zone of heating 303 is positioned on the described first phase change layer 304a;
The second phase change layer 304b is positioned on the described zone of heating 303;
The present invention adopts the selective epitaxial method to replace ion injection method of the prior art to form the zone of heating of phase transition storage, need not further to carry out annealing in process; Heating is equally distributed with particle in the zone of heating, thereby the performance of zone of heating also is uniform; The thickness of zone of heating and heating are easy to control with the content of particle, thereby can not damage the functional layer below the zone of heating.
Though the present invention discloses as above with preferred embodiment, the present invention is defined in this.Any those skilled in the art without departing from the spirit and scope of the present invention, all can do various changes and modification, so protection scope of the present invention should be as the criterion with claim institute restricted portion.
Claims (15)
1. the zone of heating preparation method of a phase transition storage is characterized in that, forms zone of heating at bottom electrode, forms zone of heating and adopts the selective epitaxial method, and the reacting gas of selective epitaxial comprises: Si atom and heating particle; Forming described zone of heating also comprises: the reacting gas of described selective epitaxial also comprises the boron ion; Adopt rpcvd to form zone of heating, and described heating particle comprises when being the Ge ion:
The semi-finished product print is cleaned, remove the impurity on the described semi-finished product print, obtain clean semi-finished product print, described semi-finished product print comprises: P type substrate; The N+ zone is positioned on the described P type substrate; Insulating medium layer is positioned at the two ends in described N+ zone; The bottom electrode of PN diode structure is on the N+ zone between the described insulating medium layer;
Described clean semi-finished product print is put into the rpcvd reaction cavity, described rpcvd reaction cavity is heated and reduces pressure and simultaneously charge into hydrogen in described rpcvd reaction cavity, make described rpcvd reaction cavity reach first temperature and first pressure;
Continuation is heated described rpcvd reaction cavity and is reduced pressure and continue charge into hydrogen in described rpcvd reaction cavity, described rpcvd reaction cavity is in first temperature and second pressure, the condition that keeps this first temperature and second pressure, and charge into hydrogen, silica-based gas, germanium base gas and selective gas simultaneously in described rpcvd reaction cavity, second pressure is less than first pressure;
When the thickness of epitaxially grown zone of heating reaches first thickness, stop in described rpcvd reaction cavity, to charge into silica-based gas, germanium base gas and selective gas and stop heating and decompression to described rpcvd reaction cavity simultaneously, make described rpcvd reaction cavity cooling;
In described rpcvd reaction cavity, take out the semi-finished product print that comprises zone of heating, finish the preparation of phase transition storage zone of heating.
2. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, the thickness range of described zone of heating is
Electrical resistivity range is 10
-5～10
2Ω cm.
3. the zone of heating preparation method of phase transition storage according to claim 1 and 2 is characterized in that, described heating comprises with particle: a kind of in Ge ion, Ta ion, W ion, Sb ion or the C atom.
4. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, the flow of described hydrogen is controlled all the time at 0.1slm to 100slm.
5. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, the scope of described first temperature comprises: 550 ℃～1100 ℃.
6. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, the scope of described first pressure comprises: 5～700 holders.
7. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, the scope of described second pressure comprises: 1～20 holder.
8. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, described silica-based gas comprises: SiH
4, SiH
2Cl
2And Si
2H
6In one or more, and the range of flow of silica-based gas comprises: 1sccm to 1000sccm.
9. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, described germanium base gas comprises: GeH
4, and the range of flow of described germanium base gas comprises: 1sccm to 1000sccm.
10. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, described selective gas comprises: HCl, and the range of flow of described selective gas comprises: 1sccm to 1000sccm.
11. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, the span of described first thickness comprises:
Extremely
12. the zone of heating preparation method of phase transition storage according to claim 1, it is characterized in that, also comprise: when in described rpcvd reaction cavity, charging into hydrogen, silica-based gas, germanium base gas and selective gas, also in described rpcvd reaction cavity, charge into boryl gas.
13. the zone of heating preparation method of phase transition storage according to claim 12 is characterized in that, described boryl gas comprises: B
2H
6, and the range of flow of described boryl gas comprises 1sccm to 1000sccm.
14. the zone of heating preparation method of phase transition storage according to claim 1 is characterized in that, described zone of heating is between described bottom electrode and phase change layer, and described phase change layer is positioned on the described zone of heating.
15. the zone of heating preparation method of phase transition storage according to claim 1, it is characterized in that, described zone of heating is between first phase change layer and second phase change layer, and described first phase change layer is positioned on the described bottom electrode, and described second phase change layer is positioned on the described zone of heating.
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