CN102403342A - Hafnium-based oxide high k gate dielectric layer and energy band adjustment and control method of hafnium-based oxide high k gate dielectric layer - Google Patents

Hafnium-based oxide high k gate dielectric layer and energy band adjustment and control method of hafnium-based oxide high k gate dielectric layer Download PDF

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CN102403342A
CN102403342A CN2010102853941A CN201010285394A CN102403342A CN 102403342 A CN102403342 A CN 102403342A CN 2010102853941 A CN2010102853941 A CN 2010102853941A CN 201010285394 A CN201010285394 A CN 201010285394A CN 102403342 A CN102403342 A CN 102403342A
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dielectric layer
gate dielectric
hfo
hafnium
sputtering
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屠海令
杜军
熊玉华
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Beijing General Research Institute for Non Ferrous Metals
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Beijing General Research Institute for Non Ferrous Metals
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Abstract

The invention relates to a hafnium-based oxide high k gate dielectric layer and an energy band adjustment and control method of the hafnium-based oxide high k gate dielectric layer. The gate dielectric layer contains HfO2 and Gd2O3; and the atomic ratio Gd/(Gd plus Hf) is 0-30 percent and is not equal to 0. The energy band adjustment and control method of the hafnium-based oxide high k gate dielectric layer comprises the following steps of: respectively placing a cleaned quartz plate substrate and a cleaned monocrystalline Si chip substrate into a radio-frequency magnetic control co-sputtering plating system and co-sputtering the Gd2O3 and the HfO2 onto the substrates under the mixed atmosphere of argon and oxygen; the sputtering power of the HfO2 is 50-120W; the sputtering power of the Gd2O3 is 0-90W and is not equal to 0, and the sputtering air pressure is 0.5-3 Pa; the sputtering time on a quartz plate is 1-1.5h; the thickness of the gate dielectric layer is 100-140 nm; the sputtering time on a Si chip is 3-20 minutes; and the thickness of the gate dielectric layer is 3-25 nm. The Gd2O3 has the energy band adjustment and control effect on the HfO2 so as to facilitate reducing the leakage current of the hafnium-based oxide gate dielectric layer.

Description

A kind of hafnium base oxide high-k gate dielectric layer and can be with regulate and control method
Technical field
The present invention relates to a kind of hafnium base oxide high-k gate dielectric layer and can be with regulate and control method.
Background technology
Since first integrated circuit in 1958 is born; The integrated level of integrated circuit whenever doubled at a distance from 18 months by the mole law; Characteristic size of its elementary cell-mos field effect transistor (MOSFET, metal oxide semiconductor field effect transistor) and grid live width and gate dielectric layer thickness also constantly dwindle in equal proportion.When si-substrate integrated circuit technical development to 32 nm technology node and when following, the equivalent gate medium oxide skin(coating) thickness (EOT, equivalent oxide thickness) that is suitable for high speed, low pressure, Low-Power CMOS device will be less than 1 nanometer.The traditional grating medium is SiO 2, its dielectric constant is 3.9.Under the effect of quantum tunneling effect, grid leakage current will be with SiO 2The reducing of gate dielectric layer thickness is index and increases.Suddenly the power consumption that increases when causing MOS device OFF state of grid leakage current increases, to performance, reliability and the very big negative effect of life-span generation of microelectronic component.Traditional Si O 2The thickness limit of gate medium has become the Si basis set and has become circuit to continue to improve the bottleneck of integrated level.One of effective ways that solve this bottleneck are to adopt high-k gate dielectric to replace traditional SiO 2, be under the condition of identical gate capacitance guaranteeing that grid have identical control ability to raceway groove, the increase of gate medium dielectric constant will make the physical thickness of gate dielectric layer increase, so the direct Tunneling electric current between grid and raceway groove will reduce greatly.
In the end of the year 2007, Intel Company has successfully introduced high k/ metal gate technique in 45 nanometer Penryn core Xeon processors of volume production, has opened up new era of new material entering conventional MOS device.Wherein noticeable is that hafnium base oxide high-k gate dielectric obtains commercial application for the first time in the conventional MOS device.
Although the hafnium base oxide has been successfully applied in the 45nm technology node of Intel; Yet; Compare with being close to perfect silicon dioxide gate medium, hafnium base oxide gate medium still exists energy gap problem less than normal and band skew (with respect to substrate such as Si base, Ge base etc.) problem of smaller.SiO 2Conduction band bottom form HfO by the 3p attitude of Si 2The conduction band electron attitude mainly form by the 5d antibonding state, so, HfO 2Energy gap less than SiO 2SiO 2Energy gap be 8.9eV, and the about 3.15eV of conduction band offset amount between the Si, the valence band offset amount is 4.65eV.HfO 2The about 5.8eV of energy gap, HfO 2The conduction band offset amount will be much smaller than the valence band offset amount, its conduction band offset amount is 1.5eV, less than SiO 23.15eV.Although it is multiple that the mechanism of grid Leakage Current has, general all be exponential relationship, so the energy gap of high-dielectric-coefficient grid medium and band side-play amount are the key factors that determines the grid Leakage Current with the band side-play amount.Therefore, the energy gap of increase hafnium base oxide helps making it to satisfy the requirement more harsh to gate medium of the following technology node of 32 nanometers with the band side-play amount.
Summary of the invention
The object of the present invention is to provide a kind of hafnium base oxide high-k gate dielectric layer, through to HfO 2In mix the Gd of appropriate amount 2O 3With the energy gap and band side-play amount that increases this gate dielectric layer.
What another object of the present invention is to provide a kind of hafnium base oxide high-k gate dielectric layer can be with regulate and control method.Through radio frequency magnetron cosputtering method, with rare earth oxide Gd 2O 3Be doped to HfO 2In, reach the Gd of different dopings 2O 3To HfO 2Can be with regulating and controlling effect, thereby help reducing the leakage current of hafnium base oxide gate dielectric layer.
For achieving the above object, the present invention adopts following technical scheme:
A kind of hafnium base oxide high-k gate dielectric layer comprises HfO 2And Gd 2O 3, Gd wherein 2O 3Incorporation be calculated as 0～30% with atomic ratio Gd/ (Gd+Hf), Gd/ (Gd+Hf) ≠ 0 wherein.
The energy gap of said gate dielectric layer is 5.81～6.00eV.
In oxidic multi-component systems, the reciprocation between transition metal that is separated from each other and rare metal sublattice causes the reduction between the similar ionic state overlapping; Around rare earth and the transition metal atoms, especially under the amorphous network scenario, symmetric reduction can cause the division that does not take attitude simultaneously; The position of not filling up 4f electronic state energy level in addition in the rare earth ion is the function of shell filling rate, and this energy level will cause the variation of oxide energy gap.
Gd 2O 3The energy gap that can make hafnium base oxide high-k gate dielectric of mixing increase with the band side-play amount, but be not Gd 2O 3Incorporation many more, HfO 2The energy gap of base high-k gate dielectric is many more with the increase of band side-play amount.Gd 2O 3Incorporation too much also can bring other influence, as make n type HfO with oxygen room 2Become p type HfO 2Gd in the hafnium base oxide high-k gate dielectric layer of the present invention 2O 3Incorporation calculate with atomic ratio Gd/ (Gd+Hf) and preferably be no more than 30%.
A kind of above-mentioned hafnium base oxide high-k gate dielectric layer can be with regulate and control method, may further comprise the steps:
(1) quartz plate substrate that cleans up or single crystalline Si sheet substrate are put into radio frequency magnetron sputter coating system altogether, through Gd 2O 3Target and HfO 2Cosputtering Gd on the target substrate 2O 3And HfO 2, HfO 2The sputtering power of target is 50～120W, Gd 2O 3The sputtering power of target is 0～90W, and this sputtering power ≠ 0, and sputter gas is the mist of argon gas and oxygen, and sputtering pressure is 0.5～3Pa, and the sputtering time on the quartz plate substrate is 1h～1.5h, and the sputtering time on Si sheet substrate is 3～20 minutes;
(2) be 100～140nm through the thickness of controlling the gate dielectric layer that forms on the sputtering time control quartz plate substrate, the thickness of the gate dielectric layer that forms on the single crystalline Si sheet substrate is 3～25nm;
The energy gap of the gate dielectric layer of (3) confirming to form on the quartz plate substrate through ultraviolet absorption spectroscopy; Adopt the phase structure of the gate dielectric layer that forms on the X-ray diffraction analysis single crystalline Si sheet substrate, adopt the composition of this gate dielectric layer of X-ray photoelectron spectroscopic analysis, prepare mos capacitance, test the current characteristics of this gate dielectric layer.
Rotation through substrate guarantees the uniformity of gate dielectric layer, and rotational velocity is 6 rev/mins, and rotating speed is high slightly or low slightly all can.Film thickness uniformity can be through at least 5 positions of step appearance test consistency or the difference of diverse location thickness of thickness check.
Said Gd 2O 3Target and HfO 2The purity of target is 99.99%.
Argon gas is 1: 10～1: 2 with the mixed volume ratio of oxygen in the said sputter gas.
Sputter gas uses the mist of argon gas and oxygen, and wherein the effect of oxygen is to reduce the HfO that coating process causes as far as possible 2Anoxic is at other condition such as Gd 2O 3Identical situation such as Doped Power under, the mixing ratio regular meeting of argon gas and oxygen is influential to the oxygen room in the gate dielectric layer, the influence different to the leakage current generating of gate dielectric layer.
Said single crystalline Si is Si (100), n type or p type, and resistivity is 2～5 Ω cm.
Said single crystalline Si sheet substrate needed to adopt the RCA method to clean before putting into the common sputter coating system of radio frequency magnetron, was placed in the HF solution again and soaked 30s, dried up with nitrogen gun then.
The invention has the beneficial effects as follows:
The present invention adopts radio frequency magnetron cosputtering method, with rare earth oxide Gd 2O 3Be doped to HfO 2In, change Gd through the sputtering power that changes target 2O 3Doping, obtain different dopings to HfO 2Can be with regulating and controlling effect, thereby help reducing the leakage current of hafnium base oxide gate medium.Doping Gd 2O 3After, HfO 2Energy gap increase, leakage current density reduces, and helps HfO 2As the application of gate medium at 32nm and following technology node.
Description of drawings
Fig. 1 is the XRD figure spectrum of the gate dielectric layer of embodiment 1 preparation.
Fig. 2 is the energy gap figure of the gate dielectric layer of embodiment 2 preparations.
Fig. 3 is the energy gap figure of the gate dielectric layer of embodiment 3 preparations.
Fig. 4 is the energy gap figure of the gate dielectric layer of embodiment 4 preparations
Fig. 5 is the I-V curve of the gate dielectric layer of embodiment 5 preparations.
Embodiment
Embodiment 1
Adopt radio frequency magnetron cosputtering method to prepare Gd 2O 3Doping HfO 2Gate dielectric layer, substrate are that resistivity is the n type single crystalline Si sheet of 4 Ω cm.The single crystalline Si sheet after adopting the cleaning of RCA method, is placed in the HF solution and soaks 30s, dry up with nitrogen gun then, put into radio frequency magnetron sputter coating system altogether, through Gd 2O 3Target and HfO 2Cosputtering Gd on the target single crystalline Si substrate 2O 3And HfO 2, HfO 2The sputtering power of target is 100W, Gd 2O 3The sputtering power of target is 40W, and sputter gas is the mist of argon gas and oxygen, and the volume ratio of oxygen and argon gas is 1: 8 in this mist, and sputtering pressure is 2Pa.Sputtering time is 20 minutes, and the thickness of gate dielectric layer is about 22nm.
Be illustrated in figure 1 as the XRD figure spectrum of the gate dielectric layer that plates, have only the monocrystalline peak of Si, show the Gd that plates 2O 3Doping HfO 2Gate dielectric layer is a non crystalline structure.
Embodiment 2
Adopt radio frequency magnetron cosputtering method to prepare pure HfO 2And Gd 2O 3Doping HfO 2Gate dielectric layer, and the two energy gap and band side-play amount relatively.Employed substrate is quartz plate and single crystalline Si sheet in the present embodiment.
The length of this quartz plate substrate is 25mm, and width is 20mm, and thickness is 1mm, and is clean through ultrasonic cleaning before using; This single crystalline Si sheet substrate select with embodiment 1 in identical single crystalline Si sheet, the quartz plate substrate is put into the common sputter coating system of radio frequency magnetron, prepare HfO respectively 2Gate dielectric layer and Gd 2O 3Doping HfO 2Gate dielectric layer.Single crystalline Si sheet substrate is put into radio frequency magnetron sputter coating system altogether, preparation Gd 2O 3Doping HfO 2Gate dielectric layer.
Prepare pure HfO 2The technological parameter of gate dielectric layer is: HfO 2The sputtering power of target is 110W, and sputter gas is the mist of argon gas and oxygen, and the volume ratio of oxygen and argon gas is 1: 6 in this mist, and sputtering pressure is 2Pa, and sputtering time is 2 hours, and the thickness of gate dielectric layer is about 120nm.
Preparation Gd 2O 3Doping HfO 2The technological parameter of gate dielectric layer is: HfO 2The sputtering power of target is 110W, Gd 2O 3The sputtering power of target is 20W, and sputter gas is the mist for argon gas and oxygen, and the volume ratio of oxygen and argon gas is 1: 6 in this mist, and sputtering pressure is 2Pa, and sputtering time is 1 hour 45 minutes, and the thickness of gate dielectric layer is about 120nm.Atomic ratio Gd/ (Gd+Hf) in the employing X-ray photoelectron spectroscopic analysis single crystalline Si sheet substrate gained gate dielectric layer composition is ≈ 8.5% (at.%).
Adopt ultraviolet absorption spectroscopy to confirm the energy gap of gained gate dielectric layer on the quartz plate substrate, as shown in Figure 2, the pure HfO of gained 2The energy gap of gate dielectric layer is 5.81eV, Gd 2O 3Doping HfO 2The energy gap of gate dielectric layer is 5.86eV, can know Gd 2O 3After the doping, HfO 2The energy gap of gate dielectric layer increases.Because HfO 2The position of valence band top energy level is mainly decided by the 2p π attitude of oxygen, so energy gap increases valence band offset is had no impact, and improves at the bottom of its conduction band, thereby cause the conduction band offset amount to increase, with HfO 2Compare Gd 2O 3Doping HfO 2The energy gap of gate dielectric layer increases 0.05eV, and then its conduction band offset is with respect to HfO 2Also increase 0.05eV, promptly be increased to 1.55eV by 1.5eV.
Embodiment 3
Adopt radio frequency magnetron cosputtering method to prepare Gd 2O 3Doping HfO 2Gate dielectric layer, substrate select with embodiment 2 in identical quartz plate and single crystalline Si sheet.
Quartz plate substrate and single crystalline Si sheet are put into radio frequency magnetron sputter coating system altogether, preparation Gd respectively 2O 3Doping HfO 2Gate dielectric layer.HfO 2The sputtering power of target is 110W, Gd 2O 3The sputtering power of target is 50W, and sputter gas is the mist of argon gas and oxygen, and the volume ratio of oxygen and argon gas is 1: 6 in this mist, and sputtering pressure is 1.5Pa, and sputtering time is 1 hour 30 minutes, and the thickness of gate dielectric layer is about 120nm.Adopt on the X-ray photoelectron spectroscopic analysis single crystalline Si sheet substrate in the gained gate dielectric layer composition (at.%) ≈ 14.1% of atomic ratio Gd/ (Gd+Hf).Adopt ultraviolet absorption spectroscopy to confirm the energy gap of gained gate dielectric layer on the quartz plate substrate, as shown in Figure 3, gained Gd 2O 3Doping HfO 2The energy gap of gate dielectric layer is 5.89eV, with the pure HfO of gained among the embodiment 2 2Gate dielectric layer is compared, and its energy gap has tangible increase.
Embodiment 4
Adopt radio frequency magnetron cosputtering method to prepare Gd 2O 3Doping HfO 2Gate dielectric layer, substrate select with embodiment 2 in identical quartz plate and single crystalline Si sheet.
Quartz plate substrate and single crystalline Si sheet are put into radio frequency magnetron sputter coating system altogether, preparation Gd respectively 2O 3Doping HfO 2Gate dielectric layer.HfO 2The sputtering power of target is 120W, Gd 2O 3The sputtering power of target is 80W, and sputtering pressure is the mist of argon gas and oxygen, and the volume ratio of oxygen and argon gas is 1: 5 in this mist, and sputtering pressure is 2Pa, and sputtering time is 1 hour 20 minutes, and the thickness of gate dielectric layer is about 120nm.Adopt on the X-ray photoelectron spectroscopic analysis single crystalline Si sheet substrate in the gained gate dielectric layer composition (at.%) ≈ 26.3% of atomic ratio Gd/ (Gd+Hf).Adopt ultraviolet absorption spectroscopy to confirm the energy gap of gained gate dielectric layer on the quartz plate substrate, as shown in Figure 4, gained Gd 2O 3Doping HfO 2The energy gap of gate dielectric layer is 5.98eV, with the pure HfO of gained among the embodiment 2 2Gate dielectric layer is compared, and its energy gap has more significantly increase.
Embodiment 5
Adopt radio frequency magnetron cosputtering method to prepare pure HfO 2And Gd 2O 3Doping HfO 2Gate dielectric layer, the substrate that uses in the present embodiment is identical with single crystalline Si sheet substrate among the embodiment 1.Single crystalline Si sheet substrate is put into radio frequency magnetron sputter coating system altogether, prepare pure HfO 2Gate dielectric layer and Gd 2O 3Doping HfO 2Gate dielectric layer.
Prepare pure HfO 2The technological parameter of gate dielectric layer is: HfO 2The sputtering power of target is 120W, and sputter gas is the mist of argon gas and oxygen, and the volume ratio of oxygen and argon gas is 1: 5 in this mist, and sputtering pressure is 2Pa, and sputtering time is 7 minutes 24 seconds, and the thickness of gate dielectric layer is about 8nm.
Preparation Gd 2O 3Doping HfO 2The technological parameter of gate dielectric layer is: HfO 2The sputtering power of target is 120W, Gd 2O 3The sputtering power of target is 80W, and sputter gas is the mist of argon gas and oxygen, and the volume ratio of oxygen and argon gas is 1: 5 in this mist, and sputtering pressure is 2Pa, and sputtering time is 5 minutes 20 seconds, and the thickness of gate dielectric layer is about 8nm.
Prepare mos capacitance, test the current characteristics of above-mentioned two kinds of gate dielectric layers.The leakage current curve is as shown in Figure 5.Can find out, when the 1V grid voltage, pure HfO 2The leakage current density of gate dielectric layer is 6.98 * 10 -4A/cm 2, doping Gd 2O 3After, leakage current is decreased to 2.16 * 10 -5A/cm 2, leakage current has reduced by 1 most magnitude.

Claims (7)

1. a hafnium base oxide high-k gate dielectric layer is characterized in that, comprises HfO 2And Gd 2O 3, Gd wherein 2O 3Incorporation be calculated as 0～30% with atomic ratio Gd/ (Gd+Hf), Gd/ (Gd+Hf) ≠ 0 wherein.
2. according to the said hafnium base oxide of claim 1 high-k gate dielectric layer, it is characterized in that the energy gap of said gate dielectric layer is 5.81～6.00eV.
The said hafnium base oxide of claim 1 high-k gate dielectric layer can be with regulate and control method, it is characterized in that, may further comprise the steps:
(1) quartz plate substrate that cleans up or single crystalline Si sheet substrate are put into radio frequency magnetron sputter coating system altogether, through Gd 2O 3Target and HfO 2Cosputtering Gd on the target substrate 2O 3And HfO 2, HfO 2The sputtering power of target is 50～120W, Gd 2O 3The sputtering power of target is 0～90W, and this sputtering power ≠ 0, and sputter gas is the mist of argon gas and oxygen, and sputtering pressure is 0.5～3Pa, and sputtering time is 1h～1.5h; Sputtering time on the quartz plate substrate is 1h～1.5h, and the sputtering time on single crystalline Si sheet substrate is 3～20 minutes;
(2) be 100～140nm through the thickness of controlling the gate dielectric layer that forms on the sputtering time control quartz plate substrate, the thickness of the gate dielectric layer that forms on the single crystalline Si sheet substrate is 3～25nm;
The energy gap of the gate dielectric layer of (3) confirming to form on the quartz plate substrate through ultraviolet absorption spectroscopy; Adopt the phase structure of the gate dielectric layer that forms on the X-ray diffraction analysis single crystalline Si sheet substrate, adopt the composition of this gate dielectric layer of X-ray photoelectron spectroscopic analysis, prepare mos capacitance, test the current characteristics of this gate dielectric layer.
4. hafnium base oxide high-k gate dielectric layer according to claim 3 can be with regulate and control method, it is characterized in that said Gd 2O 3Target and HfO 2The purity of target is 99.99%.
5. hafnium base oxide high-k gate dielectric layer according to claim 3 can be with regulate and control method, it is characterized in that argon gas is 1: 10～1: 2 with the mixed volume ratio of oxygen in the said sputter gas.
6. hafnium base oxide high-k gate dielectric layer according to claim 3 can be with regulate and control method, it is characterized in that said single crystalline Si is Si (100), n type or p type, resistivity is 2～5 Ω cm.
7. hafnium base oxide high-k gate dielectric layer according to claim 3 can be with regulate and control method; It is characterized in that said single crystalline Si sheet substrate needed to adopt the RCA method to clean before putting into the common sputter coating system of radio frequency magnetron; Be placed on again in the HF solution and soak 30s, dry up with nitrogen gun then.
CN2010102853941A 2010-09-16 2010-09-16 Hafnium-based oxide high k gate dielectric layer and energy band adjustment and control method of hafnium-based oxide high k gate dielectric layer Pending CN102403342A (en)

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CN106057642A (en) * 2016-05-27 2016-10-26 清华大学 Semiconductor structure and method for preparing semiconductor structure
CN110527978A (en) * 2019-07-25 2019-12-03 中国科学院微电子研究所 A kind of rear-earth-doped hafnium base ferroelectric material, preparation method and semiconductor devices

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CN106057642A (en) * 2016-05-27 2016-10-26 清华大学 Semiconductor structure and method for preparing semiconductor structure
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