CN101060078A - Manufacture method of HD Ru nanocrystalline sputtering deposition for flash memory - Google Patents
Manufacture method of HD Ru nanocrystalline sputtering deposition for flash memory Download PDFInfo
- Publication number
- CN101060078A CN101060078A CN 200710040770 CN200710040770A CN101060078A CN 101060078 A CN101060078 A CN 101060078A CN 200710040770 CN200710040770 CN 200710040770 CN 200710040770 A CN200710040770 A CN 200710040770A CN 101060078 A CN101060078 A CN 101060078A
- Authority
- CN
- China
- Prior art keywords
- nanocrystalline
- sputtering
- flash memory
- annealing
- dielectric constant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The sputtering-deposition preparation method for high-density nano-Ru crystal comprises: heat growing SiO2 layer or film with high dielectric constant on the Si surface, depositing 2-5nm Ru film with sputtering deposition, and fast annealing at high temperature. The product can be used to flash memory. This invention is compatible to CMOS technique, and operates simply.
Description
Technical field
The invention belongs to the semiconductor preparing process technical field, be specifically related to prepare the method for high density Ru nanocrystalline, to be used for nanocrystalline flush memory device at silica and high dielectric constant film surface.
Technical background
The expansion day by day in portable type electronic product market has stimulated the demand of people to flash memory (being flush memory device) greatly.Flash memory just develops towards the direction of high speed, low-power consumption and high storage density, and this requires the physical size of flash memory cells further to dwindle.Traditional multi-crystal silicon floating bar structure memory can't satisfy the growth requirement of following memory, because when the tunnel oxide layer thickness that links to each other with silicon substrate is reduced to several nanometer, captive electric charge is easy to turn back in the silicon substrate by tunnel oxide, thereby cause the electric charge hold function to reduce greatly, and can't satisfy actual application
[1]This just need replace traditional multi-crystal silicon floating bar flash memory structure with new structure and material.Nanocrystalline flash memory structure adopts the nano particle of semiconductor or metal to be used as the electric charge capture center, they are insulated dielectric isolation each other, the electric charge of storing in nanocrystalline can not move freely, therefore the electric charge that local defective can not cause storing in the tunnel layer runs off in a large number, and the holding time of electric charge is prolonged greatly.The thickness that this means tunnel oxide can further reduce, thereby makes nanocrystalline flush memory device become the strong replacer of embedded flash memory of future generation
[1-4]
Ruthenium (Ru) metallic nano crystal have bigger work function (～5eV), so adopt Ru can provide good charge-retention property as the electric charge capture center.In flash memory, adopt high dielectric constant to do tunnel oxide, can realize better data hold function
[4]In addition, the chemical stability between Ru and high dielectric constant is good, and itself is easy to dry etching ruthenium, and its oxide still is good conductor.So Ru is nanocrystalline to be electric charge capture material very promising in the flush memory device.
At present, the method that is used for preparing metallic nano crystal mainly is divided into two big classes: colloidal suspensions and directly deposit.The former is a chemical method, wherein relates to the employing of some chemical reagent, therefore provides potential pollutant sources, and is incompatible with CMOS technology, mainly is to be used for catalytic reaction.Directly the method for deposit comprises methods such as electron beam evaporation, sputter, ion injection, atomic layer deposition, and electron beam evaporation can not get large tracts of land even metal layer thickness, and ion injects and has very poor space controllability.
List of references
[1]H.I.Hanafi，S.Tiwari，and I.Khan，“Fast and long retention-time nano-crystal memory，”IEEE Trans.Electron Devices，vol.43，no.9，pp.1553-1558，Sep.1996.
[2]T.Usuki，T.Futatsugi，and N.Yokoyama，“A proposal of new floating-gate memory storinga small number of electrons with relatively long retention time at low voltage operations，”Microelectron.Eng.，vol.47，no.1-4，pp.281-283，Jun.1999.
[3]Z.Liu，C.Lee，V.Narayanan，G.Pei，and E.C.Kan，“Metal nanocrystal memories-Part I：Device design and fabrication，”IEEE Trans.Electron Devices，vol.49，no.9，pp.1606-1613，Sep.2002.
[4]J.J.Lee and D.-L.Kwong，“Metal nanocrystal memory with high-κtunneling barrier forimproved data retention，”IEEE Trans.Electron Devices，vol.52，no.4，pp.507-511，Apr.2005.
[5]Y A.Johansson，T.Torndahl，L.M.Ottosson，M.Boman，J.O.Carlsson，Materials Science &Engineering C.23(2003)823.
Summary of the invention
The purpose of this invention is to provide a kind of in silica and the nanocrystalline method of high dielectric constant upper film surface preparation high density Ru.
The preparation high density Ru nanocrystalline method that the present invention proposes, be adopt sputtering method at silicon oxide film and high dielectric constant (as HfO
2, Al
2O
3Deng) deposition high density Ru is nanocrystalline on the film, the nanocrystalline average diameter that obtains is 5-25nm, density is 1 * 10
11-5 * 10
12Cm
-2Size that Ru is nanocrystalline and density are controlled by metal Ru original depth and high-temperature heat treatment condition (temperature and time of rapid thermal annealing).Concrete steps are as follows:
(1) the silicon chip surface heat growth one deck SiO that is cleaning through traditional handicraft
2, or adopt the method for atomic layer deposition to grow high dielectric constant (as HfO
2, Al
2O
3Deng) film;
(2) adopt sputter (comprising ion beam sputtering and magnetron sputtering) method, sputtering deposit super thin metal Ru on the sull that in step (1), forms, thickness is 2-5nm.Used sputtering target is the ruthenium target;
(3) high-temperature quick thermal annealing, annealing temperature are 700-1000 ℃, and annealing time is 10-300 second.
The present invention has the following advantages:
(1) all processing steps are compatible mutually with CMOS technology, can not introduce pollution, and the Ru that can obtain uniformly, be the bidimensional distribution is nanocrystalline.
(2) nanocrystalline size and the density of Ru can be controlled by the temperature and time of thermal annealing after Initial R u layer thickness and the deposit, and is simple to operate.
(3) Ru nanocrystalline for preparing is applicable to flash memory.
The subordinate list explanation
Table 1 is among the embodiment 1, the nanocrystalline average diameter and the density of Ru of gained behind 900 ℃ of annealing different times.
Table 1.
| Annealing time (s) | Average diameter (nm) | Density (* 10 11cm -2) |
| 15 | 20 | 1.6 |
| 30 | 21 | 1.4 |
| 45 | 22 | 1.3 |
| 120 | 20 | 1.5 |
| 300 | 22 | 1.5 |
Description of drawings
Fig. 1 is among the embodiment 1, the metal Ru that adopts ion beam sputtering to obtain, after the nanocrystalline diameter distribution map of the Ru that obtains through 900 ℃ of annealing 15s (selected sample area is 760nm * 570nm).
Embodiment
Embodiment 1
After adopting the traditional handicraft cleaning silicon chip, with the high dielectric constant Al of atomic layer deposition method growth 3nm
2O
3, the reaction source that is adopted is trimethyl aluminium and water.Then, adopt ion beam sputtering method at Al
2O
3The ultra-thin ruthenium metal layer of last deposit, sputter rate were 1 dust/second, and sputtering time is 45 seconds.Carry out rapid thermal annealing under the different temperatures subsequently in 700-1000 ℃ of scope, annealing time is controlled at 15-300 second.When annealing conditions be 900 ℃, during 15s, the nanocrystalline density of the Ru that obtains is 1.6 * 10
11Cm
-2, average diameter is 20nm.The nanocrystalline diameter Distribution Statistics of concrete Ru has shown that nanocrystalline diameter distribution is narrower, and has been Gaussian Profile as shown in Figure 1.Table 1 listed 900 ℃ down different annealing times to the nanocrystalline diameter of Ru and the influence of density.The variation of annealing time is little to the size and the density influence of Ru nanocrystalline as can be seen from the table.Resulting Ru nanocrystalline has high density and equally distributed characteristics in this example, can be applicable in the nanocrystalline flash memory.
Claims (2)
1, a kind of sputtering sedimentation preparation method who is applicable to the high density Ru nanocrystalline of flash memory is characterized in that concrete steps are as follows:
(1) the silicon chip surface heat growth one deck SiO that is cleaning through traditional handicraft
2, or the method growth high dielectric constant film of employing atomic layer deposition;
(2) adopt sputtering method, sputtering deposit super thin metal Ru on the sull that in step (1), forms, thickness is 2-5nm, used sputtering target is the ruthenium target;
(3) high-temperature quick thermal annealing, annealing temperature are 700-1000 ℃, and annealing time is 10-300 second.
2,, it is characterized in that described high dielectric constant is HfO according to the described sputtering sedimentation preparation method who is applicable to the high density Ru nanocrystalline of flash memory of claim
2Or Al
2O
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100407709A CN100477095C (en) | 2007-05-17 | 2007-05-17 | Manufacture method of sputtering deposition of high-density Ru nanocrystalline for flash memory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100407709A CN100477095C (en) | 2007-05-17 | 2007-05-17 | Manufacture method of sputtering deposition of high-density Ru nanocrystalline for flash memory |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101060078A true CN101060078A (en) | 2007-10-24 |
| CN100477095C CN100477095C (en) | 2009-04-08 |
Family
ID=38866093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100407709A Expired - Fee Related CN100477095C (en) | 2007-05-17 | 2007-05-17 | Manufacture method of sputtering deposition of high-density Ru nanocrystalline for flash memory |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100477095C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101692463B (en) * | 2009-09-24 | 2011-12-14 | 复旦大学 | Capacitor structure of mixed nano-crystal memory and preparation method thereof |
| CN101807521B (en) * | 2009-02-13 | 2012-03-07 | 中国科学院微电子研究所 | Method for preparing of compound trapping layer in floating gate type nonvolatile storage |
| CN107304471A (en) * | 2016-04-22 | 2017-10-31 | 江苏科技大学 | It is a kind of in ruthenium film of molybdenum deposition on substrate and preparation method thereof |
| CN109037220A (en) * | 2018-06-25 | 2018-12-18 | 浙江师范大学 | A kind of method of low temperature preparation tin nano-crystal memory |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894753B (en) * | 2010-07-08 | 2012-10-17 | 复旦大学 | Method for preparing dielectric film embedded with high-density palladium nano-crystal |
-
2007
- 2007-05-17 CN CNB2007100407709A patent/CN100477095C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807521B (en) * | 2009-02-13 | 2012-03-07 | 中国科学院微电子研究所 | Method for preparing of compound trapping layer in floating gate type nonvolatile storage |
| CN101692463B (en) * | 2009-09-24 | 2011-12-14 | 复旦大学 | Capacitor structure of mixed nano-crystal memory and preparation method thereof |
| CN107304471A (en) * | 2016-04-22 | 2017-10-31 | 江苏科技大学 | It is a kind of in ruthenium film of molybdenum deposition on substrate and preparation method thereof |
| CN109037220A (en) * | 2018-06-25 | 2018-12-18 | 浙江师范大学 | A kind of method of low temperature preparation tin nano-crystal memory |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100477095C (en) | 2009-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7504280B2 (en) | Nonvolatile memory device and method of manufacturing the same | |
| CN101252148B (en) | Nonvolatile memory electronic device and its manufacture method | |
| CN101692463B (en) | Capacitor structure of mixed nano-crystal memory and preparation method thereof | |
| CN100477095C (en) | Manufacture method of sputtering deposition of high-density Ru nanocrystalline for flash memory | |
| Liou et al. | RETRACTED: Growth behavior and microstructure evolution of ZnO nanorods grown on Si in aqueous solution | |
| CN1979828A (en) | Metal silicide nano-wire and its making method | |
| Fu et al. | ZnS nanodot film as defect passivation layer for Cu (In, Ga)(S, Se) 2 thin‐film solar cells deposited by spray‐ILGAR (ion‐layer gas reaction) | |
| CN103700576A (en) | Preparing method of self-assembly forming-dimension-controllable silicon nanocrystal films | |
| CN102290435A (en) | Large-area perfect quantum dot and manufacturing method of array thereof | |
| CN100477094C (en) | Manufacture method of atomic layer deposition of high-density Ru nanocrystalline for flash memory | |
| Qi et al. | SiGe nanowire growth and characterization | |
| CN100418196C (en) | Process for producing single-orientation ferroelectric thin film with double-axle texture MgO as buffer layer | |
| JP2010232657A (en) | Method for manufacturing memory device | |
| US20110198680A1 (en) | Non-Volatile Memory Device Including Quantum Dots Embeded in Oxide Thin Film, and Fabrication Method of the Same | |
| CN108022694B (en) | A kind of preparation method of transparent conductive oxide film-nanometer line network | |
| CN101908477B (en) | Method for preparing gate stack of metallic nano crystal memory | |
| CN101901755B (en) | Method for preparing high-density palladium nanocrystal suitable for flash memory | |
| CN101894753B (en) | Method for preparing dielectric film embedded with high-density palladium nano-crystal | |
| CN111312806B (en) | Preparation method and product of single-layer atomic channel fin field effect transistor | |
| CN103147046A (en) | Preparation method of tin dioxide semiconductor film and defect annihilation method thereof | |
| CN101740522B (en) | Method for preparing high-density cobalt nano dots suitable for flash memory device | |
| CN101369607B (en) | Flash memory unit structure and preparation thereof | |
| CN108493095B (en) | Charge trap memory device with double-layer oxide nanocrystalline memory layer and preparation method thereof | |
| Benner et al. | Semiconductor nanocrystals embedded in high-k materials | |
| Wang et al. | Preparation of NiFe binary alloy nanocrystals for nonvolatile memory applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090408 Termination date: 20140517 |