CN104851791A - Method for depositing high-K gate dielectric on atomic layer on surface of graphene - Google Patents
Method for depositing high-K gate dielectric on atomic layer on surface of graphene Download PDFInfo
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- CN104851791A CN104851791A CN201510210826.5A CN201510210826A CN104851791A CN 104851791 A CN104851791 A CN 104851791A CN 201510210826 A CN201510210826 A CN 201510210826A CN 104851791 A CN104851791 A CN 104851791A
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- gate dielectric
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- graphenic surface
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Abstract
The invention discloses a method for depositing high-K gate dielectric on an atomic layer on the surface of graphene, comprising the following steps: preparing a graphene material with a clean and smooth surface and few defects as a substrate sample for depositing high-k gate dielectric; putting the substrate sample in an ALD reaction chamber, and remotely controlling rays to make electron absorption energy of a P orbit of graphene jump, change outer electron orientation, damage a delocalized large-Pai bond and form a dangling bond; feeding water vapor to complete chemical adsorption on the surface of graphene until the surface of the substrate is saturated; and feeding a first precursor source to complete high-k gate dielectric deposition on the surface of graphene. According to invention, gamma rays are used to excite electrons and damage a delocalized large-Pai bond so as to improve the surface activity of graphene. The method for depositing high-K gate dielectric on an atomic layer on the surface of graphene is simple to implement and reliable. By adopting the method, a continuous, uniform and closely-combined high-k gate dielectric layer can be formed directly on the surface of graphene.
Description
Technical field
the invention belongs to carbon back integrated circuit fields, be specifically related to one and utilize rays excite electronics, in the method for graphenic surface ald high-k gate dielectric.
Background technology
along with the development of integrated circuit fields, microelectronic device size reduces day by day, and original si-substrate integrated circuit development arrival bottleneck adopted, while reducing processing live width, the performance of degradation product may not realize hardly.The anxious application yet-to-be developed of more excellent new material.
for reducing device size while the better integrated circuit (IC)-components of acquisition, Graphene is sent to great expectations as a kind of new material, and its superhigh current carrying transport factor, outstanding mechanical property, thermal stability and good characteristic of semiconductor make Graphene become carbon back integrated circuit focus of new generation.Graphene is a kind of monolayer carbon atom film of two-dimensional structure SP2 hydridization, its S layer orbital electron is electronics cloud form, three Θ keys are formed between each atom and other three carbon atoms, its P track dumbbell shaped is perpendicular to two dimensional surface, the large π key of electronics composition delocalization on the P track of the atom of three or more, being free between each atom. the performance of its excellence, unique structure makes it very likely replace silicon, becomes leading semiconductor material of new generation.
but, on grapheme material, deposited high-k material also faces two Railway Project: 1) the large π key of graphenic surface causes it except edge, not having can the necessary dangling bonds in chemisorbed precursor source, and chemical property torpescence, directly cannot deposit high-k gate dielectric on Graphene; 2) in order to deposit high-k gate dielectric on Graphene, generally before deposition preliminary treatment is carried out to Graphene.But these pretreated methods comprise applying extra electric field, depositing metal Seed Layer, depositing either amorphous carbon-coating etc.The electron beam evaporation of general employing be carry out preliminary treatment by plated metal Seed Layer on Graphene to Graphene, but this method can cause comparatively macrolesion to Graphene lattice.Some methods are that shortcoming is that process is loaded down with trivial details at smooth flawless graphenic surface regrowth one deck island Graphene, and in growth course, can not ensure the good contact of metal used and bottom Graphene when growing.And in ALD reaction chamber the method for added electric field, can become difficult because of the restriction of ALD consersion unit itself, be difficult to truly realize.In addition, adopting scanning electron microscopy (SEM) to grow amorphous c film needs extra machinery equipment, and cost is higher.
Summary of the invention
the defect of technology existence in view of the above, the present invention seeks to: a kind of method that graphenic surface ald high-K gate dielectric is provided, the method is intended to destroy the large π key of graphenic surface, avoid resilient coating to the damage of Graphene, reduce gate dielectric layer thickness, and Graphene is impacted very little, Graphene lattice damage can not be caused, simple.And high energy particle can penetrate the wire chamber of ALD, processes Graphene.The time of this process is controlled, can complete within the set time, also can along with the deposition process of whole high-k gate dielectric.
technical scheme of the present invention is: a kind of method of graphenic surface ald high-K gate dielectric, comprises the following steps:
(1) substrate sample of grapheme material as deposition high-k gate dielectric of smooth, the few defect of surface clean is prepared;
(2) substrate sample is put into ALD reaction chamber, remote control ray, make Graphene P orbital electron absorb energy jump, change outer-shell electron orientation, destroy the large π key of delocalization, form dangling bonds;
(3) pass into steam, complete the chemisorbed of graphenic surface, until substrate surface reaches capacity;
(4) pass into the first precursor source, complete the high-k gate dielectric deposition of graphenic surface.
further, described grapheme material adopt CVD or mechanical stripping legal system standby.
further, described ray is gamma ray.
further, described gamma ray provides energy at 1-500eV.
further, described first precursor source is one or more in IIIA race metallic compound or IIIB compounds of group.
further, pass into the second precursor source after step (4), complete the doping of high-k gate dielectric.Described second precursor source is the precursor source of the IVB compounds of group such as three (tetramethyl acetone in heptan two) lanthanum, four (dimethylamino) zirconium, four (dimethylamino) hafniums or four (ethylamino-) zirconium.
further, described high-k gate dielectric layer is
,
,
,
, ZrO
2
in one or more.
the present invention utilizes gamma ray excitation electron, in the method for graphenic surface deposition high-k gate dielectric, increase electron energy on carbon atom P track, make it transition thus destroy the large π key of delocalization, strengthen graphenic surface active, ald high-k gate dielectric directly can be carried out at graphenic surface, simplify technological process, reduce the destruction of Graphene lattice and the impact on Graphene performance.Meanwhile, gamma ray provides the energy on all P tracks required for electron transition, improves the chemism of graphenic surface, thus facilitates the combination between high-k gate dielectric and graphene layer.Uniformity and the continuity of the film obtained in this way are better, graphene layer as substrate also confiscates destruction, therefore electric property is not also affected, and this makes functional being expected to of graphene device obtained obtain overall application in the manufacture of carbon back large-scale circuit.
advantage of the present invention is:
1) proposed by the inventionly gamma ray excitation electron is utilized, destroy the large π key of delocalization, improve graphenic surface active, in the method for graphenic surface ald high-k gate dielectric, this that method is simple is reliable, directly can form continuous, even, compact high-k gate dielectric layer at graphenic surface.
2) to avoid knowing clearly the introducing of resilient coating, reduce the thickness of whole graphene device.
3) this method is little to Graphene lattice damage, little to Graphene damage influence, the maximum using premium properties of Graphene.
4) easy to operate, be easy to realize, repeatability is strong.
Accompanying drawing explanation
below in conjunction with drawings and Examples, the invention will be further described:
fig. 1 is S track and vertical with two dimensional surface six P track schematic diagrames between Graphene six carbon atom;
fig. 2 is the operational flowchart of the method for graphenic surface ald high-K gate dielectric of the present invention;
fig. 3 to Fig. 6 provided by the inventionly utilizes gamma ray excitation electron, at the process chart of the direct ald high-k gate dielectric of graphenic surface.
wherein: 101, Si substrate, 102,
film, 103, graphene film, 104, gamma ray, 105,
group, 106,
gate dielectric layer.
Embodiment
for making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with embodiment also with reference to accompanying drawing, the present invention is described in more detail.The present embodiment is for only to grow Al
2
o
3
gate dielectric layer, but this dielectric layer is not adulterated.Should be appreciated that, these describe just exemplary, and do not really want to limit the scope of the invention.In addition, in the following description, the description to known features and technology is eliminated, to avoid unnecessarily obscuring concept of the present invention.
fig. 1 is S track and vertical with two dimensional surface six P track schematic diagrames between Graphene six carbon atom.
in this example, ray used is gamma ray but is not limited to gamma ray, can also adopt other ray, uses method of the present invention.
as shown in Figure 2,3, first, Si substrate 101 grows one deck
film 102, then graphene film is transferred to
surface, forms graphene film 103.
then, sample is put into ALD reaction chamber, gamma ray 104 can be launched to reduce ray to human injury by remote control, carbon atom outer P orbital electron ionization transition is excited by gamma ray, destroy the large π key of delocalization, strengthen graphenic surface active, formed and supply dangling bonds needed for ald, as shown in Figure 4.
then, by ald at graphenic surface ald high-k gate dielectric.The present embodiment is at 100-200 temperature, first passes into the first precursor source
, complete chemisorbed at graphenic surface, formed
group 105, unnecessary trimethyl aluminium and gaseous reaction product are taken away by carrier gas, then pass into
, with graphenic surface chemisorbed before
group 105 learns reaction, after repeating these two certain number of times of step, can go out the continuous, evenly, closely of suitable thickness in graphene film 103 superficial growth
high-k gate dielectric layer 106, as seen in figs. 5-6.The high-k gate dielectric layer that can grow is
,
,
,
in one or more.
in this example, the first precursor source is trimethyl aluminium.In addition, can also be the IIIA race metallic compounds such as Al, the IIIB race metallic compounds such as La, Gd.
the high-k gate dielectric layer deposited in the present embodiment does not adulterate.If need to adulterate to high-k gate dielectric layer, then whole preparation process is except using steam and the first precursor source, also will add the second precursor source according to one or both elements of doping.
second precursor source is one or more of the IVB compounds of group such as Hf, Zr, Ti is one or more.
in addition can also continue as required to pass into precursor source, complete more complicated doping.
should be understood that, above-mentioned embodiment of the present invention only for exemplary illustration or explain principle of the present invention, and is not construed as limiting the invention.Therefore, any amendment made when without departing from the spirit and scope of the present invention, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.In addition, claims of the present invention be intended to contain fall into claims scope and border or this scope and border equivalents in whole change and modification.
Claims (9)
1. a method for graphenic surface ald high-K gate dielectric, is characterized in that, comprises the following steps:
(1) substrate sample of grapheme material as deposition high-k gate dielectric of smooth, the few defect of surface clean is prepared;
(2) substrate sample is put into ALD reaction chamber, remote control ray, make Graphene P orbital electron absorb energy jump, change outer-shell electron orientation, destroy the large π key of delocalization, form dangling bonds;
(3) pass into steam, complete the chemisorbed of graphenic surface, until substrate surface reaches capacity;
(4) pass into the first precursor source, complete the high-k gate dielectric deposition of graphenic surface.
2. the method for graphenic surface ald high-K gate dielectric according to claim 1, is characterized in that, described grapheme material adopts CVD, epitaxial growth method or mechanical stripping legal system standby.
3. the method for graphenic surface ald high-K gate dielectric according to claim 1, is characterized in that, described ray is gamma ray.
4. the method for graphenic surface ald high-K gate dielectric according to claim 3, it is characterized in that, described gamma ray provides energy at 1-500eV.
5. the method for graphenic surface ald high-K gate dielectric according to claim 1, is characterized in that, described first precursor source is one or more in IIIA race metallic compound or IIIB compounds of group.
6. the method for graphenic surface ald high-K gate dielectric according to claim 1, is characterized in that, pass into the second precursor source after step (4), complete the doping of high-k gate dielectric.
7. the method for graphenic surface ald high-K gate dielectric according to claim 6, is characterized in that, described second precursor source is one or more of IVB compounds of group.
8. the method for the graphenic surface ald high-K gate dielectric according to claim 6 or 7, it is characterized in that, described second precursor source is three (tetramethyl acetone in heptan two) lanthanum, four (dimethylamino) zirconium, four (dimethylamino) hafniums or four (ethylamino-) zirconium.
9. the method for graphenic surface ald high-K gate dielectric according to claim 1, it is characterized in that, described high-k gate dielectric layer is
,
,
,
, one or more in ZrO2.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106531613A (en) * | 2016-04-22 | 2017-03-22 | 中国科学院微电子研究所 | Modifying and processing method and device for selected area on graphene surface |
| CN106783560A (en) * | 2016-12-27 | 2017-05-31 | 中国科学院微电子研究所 | A kind of Graphene chemical modification method |
| WO2017096626A1 (en) * | 2015-12-11 | 2017-06-15 | 华为技术有限公司 | Method for forming gate dielectric on graphene surface and producing transistor |
| CN107768255A (en) * | 2017-10-20 | 2018-03-06 | 武汉大学 | The preparation method of low temperature thin film transistor |
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| CN102097297A (en) * | 2010-11-16 | 2011-06-15 | 复旦大学 | Method for depositing high k gate dielectrics on atomic layer on graphene surface by adopting electric field induction |
| US20120141799A1 (en) * | 2010-12-03 | 2012-06-07 | Francis Kub | Film on Graphene on a Substrate and Method and Devices Therefor |
| US20140284552A1 (en) * | 2013-03-20 | 2014-09-25 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Graphene base transistor with reduced collector area |
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2015
- 2015-04-29 CN CN201510210826.5A patent/CN104851791A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102097297A (en) * | 2010-11-16 | 2011-06-15 | 复旦大学 | Method for depositing high k gate dielectrics on atomic layer on graphene surface by adopting electric field induction |
| US20120141799A1 (en) * | 2010-12-03 | 2012-06-07 | Francis Kub | Film on Graphene on a Substrate and Method and Devices Therefor |
| US20140284552A1 (en) * | 2013-03-20 | 2014-09-25 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Graphene base transistor with reduced collector area |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017096626A1 (en) * | 2015-12-11 | 2017-06-15 | 华为技术有限公司 | Method for forming gate dielectric on graphene surface and producing transistor |
| CN106531613A (en) * | 2016-04-22 | 2017-03-22 | 中国科学院微电子研究所 | Modifying and processing method and device for selected area on graphene surface |
| CN106531613B (en) * | 2016-04-22 | 2020-07-17 | 中国科学院微电子研究所 | Selective modification processing method and device for graphene surface |
| CN106783560A (en) * | 2016-12-27 | 2017-05-31 | 中国科学院微电子研究所 | A kind of Graphene chemical modification method |
| CN107768255A (en) * | 2017-10-20 | 2018-03-06 | 武汉大学 | The preparation method of low temperature thin film transistor |
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