Applied Surface Science 227 (2004) 306311

Photoluminescence of Er-doped hydrogenated amorphous silicon nitride

Q. Zhaoa,*, H. Yanb, M. Kumedac, T. Shimizuc
b

Institute of Semiconductors, Chinese Academy of Sciences, P.O. Box 912, 100083 Beijing, PR China The Key Laboratory of Advanced Functional Material of China Educational Ministry, Beijing University of Technology, 100022 Beijing, PR China c Department of Electrical, Electronic and Computer Engineering, Kanazawa University, 920-8667 Kanazawa, Japan Received 14 November 2003; received in revised form 4 December 2003; accepted 4 December 2003

Abstract Er photoluminescence (Er PL) and dangling bonds (DBs) of annealed Er-doped hydrogenated amorphous silicon nitride (aSiN:H(Er)) with various concentrations of nitrogen are studied in the temperature range 62300 K. Post-annealing process is employed to change the DBs density of a-SiN:H(Er). PL spectra, DBs density and H, N concentrations are measured. The intensity of Er PL displays complicated relation with Si DBs density within the annealing temperature range 200500 8C. The intensity of Er PL rst increases with decreasing density of Si dangling bonds owing to the structural relaxation up to 250 8C, and continues to increase up to 350 8C even though the density of Si DBs increases due to the improvement of symmetry environment of Er3. # 2003 Elsevier B.V. All rights reserved.
PACS: 68.55.Ln; 78.55.Qr; 81.05.Ge; 81.15.Cd; 81.40.Ef Keywords: Er-doped; Photoluminescence; a-Si; Co-sputtering; Annealing

1. Introduction Erbium doped semiconductors have drawn great interest for possible optoelectronic applications owing to photoluminescence (PL) at 1540 nm, dening the so-called third spectral window, for the application in the silica optical ber communication [1]. This prospect is especially attractive in the case of indirect-gap silicon due to the enormous technological benet that would result from silicon based photonic
Corresponding author. Tel.: 86-108230-4100; fax: 86-108230-4100. E-mail address: qzhao@red.semi.ac.cn (Q. Zhao).
*

technology. The Er3 produces separated J-multiplets with 4 I15=2 and 4 I13=2 as the fundamental and the rst excited states, respectively. Because of the effective shielding of 4f electrons by the closed external Xe-like 5s25p6 shells, the matrix material has a very limited inuence on the internal 4f transitions. It is well known that the ff transitions are electric dipole forbidden in the free ion and become at least partially allowed when different angular momentum are incorporated into the f wave functions in a solid matrix. This admixture vitally depends on the immediate vicinity of the erbium ion and its symmetry. Due to the disorder of the amorphous material the symmetry of the Er environment is weaker and no solubility limit

0169-4332/$ see front matter # 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2003.12.005

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Table 1 The deposition pressure, the rf power, the substrate temperature, ow rate of sputtering gas and the deposition time for a-SiN:H(Er) prepared by rf magnetron sputtering Sample Deposition pressure (Pa) 3.3 3.3 3.3 3.3 3.5 RF power (W) Substrate temperature (8C) Flow rate of sputtering gas (sccm) Ar I II III IV V 2.0 2.0 2.0 2.0 2.2 N2 0.6 0.8 1.1 0.9 1.1 H2 0.5 0.5 0.5 0.5 0.4 Deposition time (min)

200

200

15

of Er, a-Si:H structure presents a particular advantage. Therefore, a-Si:H lms are superior to its crystalline counterpart as the Er PL host materials since a higher PL intensity at room temperature, smaller temperature quenching, and shorter lifetime of Er ions. The addition of a light element co-dopant such as C, O or F strongly increases the luminescence intensity [2,3]. These light elements are important for breaking the local symmetry of Er3 environment. Excitation of Er3 seems to be nonresonant because the intensity of Er PL pumping with appropriate lines of Ar laser shows no enhancement in amorphous silicon [4]. Fuhs et al. had proposed that electrons that recombine on Si DBs transfer their energy nonradiatively to closely neighbored Er3. This defect related Auger excitation (DRAE) depends on the capture rate of electrons by DBs near Er3 ions and on the transition dipole moments of f shell transitions. In this model, Si DBs have an essentially important role to active Er ions. The introduction of nitrogen also increases the defect density and shifts the Fermi level. The inuence of defects on the Er PL was investigated in many references [58]. But up to now, the understanding of the process is far from complete. In this study, we investigate the relation between the intensity of Er PL and the density of Si DBs in N co-doping aSi:H(Er) with post annealing procedure prepared by rf magnetron co-sputtering.

2. Experimental The samples of a-SiN:H(Er) for this study are prepared by rf magnetron co-sputtering where gas mixtures of Ar, N2 and H2 are used as sputtering gas. The lms are deposited on substrates of silica

for electron spin resonance (ESR) and optical measurements, highly resistive Si crystals for IR measurements and aluminium for PL measurements. Table 1 shows the primary deposition conditions for the samples of a-SiN:H(Er) used in this study. The nitrogen content as determined from electron probe micro analyze (EPMA) is in the range 031 at.%. The hydrogen incorporates mostly in monohydrite conguration at the IR spectroscopy absorption band of 630 cm1, but the stretching mode at 3300 cm1 of NH is also observed in some samples with high N doping content. Considering all the possible boding conguration, the hydrogen content is amounted to 17.724 at.% by Fourier transform infrared (FTIR) spectroscopy using A % 2:1 1019 cm2 [9]. The incorporation of doping Er in a-SiN:H(Er) is attained through two-step sputtering: First we prepared thick a-Si(Er) lms by putting Er chips on the target of crystalline Si wafer. Then we cut and attach these lms on the Si target and sputtering again. Er ions are distributed homogeneously in the lms of 0.550.83 mm thickness. The concentration of incorporated Er is estimated to be 0.05 at.% by EPMA. In order to obtain samples with various amounts of the density of Si DBs, the samples are annealed at different temperatures after deposition. Annealing have been done in a ow of N2 gas at the temperature from 200 to 500 8C for 30 min, respectively. The photoluminescence spectra are measured in the temperature range from 62 to 300 K with excitation by HeNe laser radiation with wavelength l 633 nm for sample IIV. The excitation power is equal to 26 mW in all cases. Argon laser (488 nm) is employed to excite sample V (N: 31 at.%) because photon energy of HeNe laser (1.96 eV) is lower than the optical gap of sample V (2.21 eV). A liquid-nitrogen

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cooled germanium detector with use of a double monochromator is applied to detect the photoluminescence. Since the optical gap is changed by the amount of hydrogen in the sample as shown in the next section, the PL intensity should be corrected by considering the difference in the absorption of the excitation light in the sample. Si DBs density is estimated by standard ESR measurements operating in X-band (9.45 GHz). The experiments are carried out at room temperature. The optical properties of the samples are monitored using the following optical parameters: Eg (optical gap) and B1/2 (slope of the optical absorption edge). Here Eg is the optical forbidden gap determined by the Tauc procedure, B1/2 is the slope of the spectral dependence of the absorption coefcient in the Tauc coordinates.

Sample I (N:0 at.%)

62K PL intensity (arb.units)

II (N:1.2 at.%)

III (N:6.3 at.%)

IV (N:16 at.%)

V (N:31 at.%)

0.7

0.8

0.9

1.0

1.1

1.2

Photon energy (eV)

3. Results and discussion In Table 2 we show the N contents, the H contents, the density of Si DBs, Eg, B1/2 and lm thickness for the samples prepared by varying the ow rate of N2 gas without post thermal annealing. H content is about to 18 at.%, and is approximately independent of the N content. Si DBs density increases with the increase of N doping content. Sixty-two kelvin PL spectra for as-prepared samples with different N content are represented in Fig. 1. Both Er3 4f-intra transition and the intrinsic emission of amorphous Si matrix are observed. The latter is presented as a broad band at 0.91.3 eV [5]. Because less erbium is incorporated in our specimens, however, sample III, IV also exhibit distinct defect-related emission at 0.80.9 eV that result from radiative
Fig. 1. Photoluminescence spectra of a-SiN:H(Er) with varying nitrogen contents at 62 K.

recombination of electrons in the conduction band tail, and holes in dangling bonds [10]. Er-induced emission at 0.8 eV dominates the spectra in Fig. 1, which with a long tail to low energy and a sharp onset at higher energy. The peak of the Er luminescence band has an unconspicuous shift following the increase of N content incorporated into a-SiN:H(Er). As well known, intra-f transition 4 I13=2 ! 4 I15=2 of Er3 can emit light at 1.54 mm (0.8 eV). The energy level positions of 4 I13=2 , 4 I15=2 have been inuenced greatly by network structure of amorphous matrix and Stark level-splitting. The Er3 in a-SiN:H(Er) is more apt to distribute in low energy state of Stark level at low temperature. Therefore, the PL spectra became

Table 2 The N contents, the H contents, the density of Si DBs, Eg, B1/2 and lm thickness for the a-SiN:H(Er) samples (as-deposition) prepared by rf magnetron sputtering with varying the ow rate of N2 gas Sample I II III IV V N content (at.%) 0 1.2 6.3 16 31 H content (at.%) 18.0 17.7 24.0 18.6 19.0 DBs density (cm3) 6.5 6.2 1.8 2.0 4.6 1017 1017 1018 1018 1018 Eg (eV) 1.56 1.59 1.68 1.61 2.21 B1/2 (eV1/2 cm1/2) 796 809 813 695 328 Films thickness (mm) 0.60 0.65 0.55 0.60 0.83

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RT 100K 62K

0.70

0.75

0.80

0.85

Photon energy (eV)

Fig. 2. The Er PL spectra of as-prepared sample V (N: 31 at.%) at different measuring temperatures.

sharper as the PL measurement temperature decrease. Fig. 2 shows the Er PL spectra of sample V at different measuring temperature. It is signicant that variation of the temperature cause dramatic changes in the wave shapes of Er PL. We calculate the areas of PL spectra to compare the PL intensities against the change of measuring temperature. All the PL intensities mentioned below are characterized by the areas of whole wave shapes. The temperature dependence of the intensity of the erbium-induced photoluminescence in a-SiN:H(Er) is shown in Fig. 3. It demonstrates that there are two different regimes: above 150 K, the intensity of the Er PL decreases sharply with increasing the temperature because of the effect of the thermal quenching, but it
10
5

decreases only slightly at the low temperature. The temperature quenching of the photoluminescence of our samples is relatively small when compared to crystalline silicon. According to the model of DRAE, the temperature dependence favors an interpretation that an enhancement of nonradiative recombination that the energy of electronhole recombination at defects is transferred to erbium ions [5]. The schematic diagram of DRAE model is shown in Fig. 4. The above result of Fig. 3 also demonstrates that the intensity of erbium-induced photoluminescence is pronouncedly inuenced by N doping-content in aSi:H. The Er PL intensity of sample with 31 at.% N concentration maintains about 0.8% of that of no nitrogen-doping counterpart at 62 K, which is about 10% at 300 K due to the different amount of the thermal quenching. The temperature dependence of the erbium emission turns much weaker with increasing nitrogen doping-content in the amorphous matrix. Note that the defect density increases with increasing nitrogen doping content as shown in Table 2, the introduction of N-ions into amorphous matrix cripples the intensity of erbium-related photoluminescence greatly. In our opinion, this relation is due to a change in the local environment of erbium ion, which attests to excitation of erbium ions via defects. Fig. 5 shows the dependence of Si DBs density on annealing temperature for the sample with nitrogen content 1.2 at.%. The structural rearrangement occurring in the course of annealing seems rather apparent. It is well-known that annealing process at 300400 8C
62 K

Er PL intensity (arb.units)

300 K 200 K

100 K

Er PL intensity (rel.units)

10

I (N : 0 at.%) II (N : 1.2 at.%) III (N : 6.3 at.%) IV (N : 16 at.%) V (N : 31 at.%)

10

10

10
-1

12

14

16

18

1000/T (K )
Fig. 3. The temperature dependences of the intensities of the as-prepared erbium-induced photoluminescence in a-SiN:H(Er) with various nitrogen contents.

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a-Si:H C.B.

Er3+
4

C.B.tail

I13/2

Auger Process
1 2 3 Er PL

DB
Intrinsic PL (0.9-1.3eV) 1 V.B.tail
4

(0.8eV)

I15/2

V.B.

Fig. 4. Schematic diagram of DRAE model. 1 and 10 is the non-radiative process of free carriers happens at Si DBs sites; 2 is the excitation process intrinsic luminescence of a-Si:H at 0.91.3 eV; 3 is the DRAE excitation process of Er3 ions at 0.8 eV.

can release hydrogen atoms from a-Si:H due to the breaking of weak SiHSi bonds in the network of the amorphous matrix. Thermal annealing result in complete saturation of chemical bonds for all constituent atoms, if the original structure is structural close to equilibrium state [11]. The intensity dependence of the erbium-induced PL at room temperature as a function of the Si DBs

concentration determined from the ESR data is plotted in Fig. 6. It is observed that the Er-related PL intensity has a fairly good correlation with the Si DBs density except for the case of the annealing at temperatures in the range of 250350 8C. In the frame of DRAE, the energy transfer from amorphous host to Er3 takes

RT Er PL intensity (rel.units)

10

350 C 300 C 250 C

o o

400 C

Dangling bond density (cm )

10

19

450 C

-3

500 C

10

10

18

200 C

10 17 10

10

18

10
-3

19

10

17

as-depo.

300

400
o

500

Dangling bond density (cm )

Fig. 6. Intensity of the Er-related PL at room temperature vs. Si DBs density detected by ESR for the sample same as shown in Fig. 5. Annealing temperatures are shown in the gure for a series of the annealed sample. Lines are drawn as guides for eye.

Annealing temperature ( C)
Fig. 5. The Si DBs density vs. annealing temperature for the sample II (N: 1.2 at.%) with nitrogen content 1.2 at.%.

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place via an Auger process as the process 3 shown in Fig. 4. The photoexcited electrons and holes are sequentially captured by nonradiative tunneling to Si DBs centers at low temperature. The nonradiative recombination rate of carriers competes with the erbium excitation rate. Hence the main origin of the decrease in the intensity of the Er PL with an increase in the density of Si DBs is due to the domination of this nonradiative tunneling in the a-SiN:H(Er). The potential liability of the a-Si:H structural network favors both a reduction in the density of nonradiative recombination centers and a change in the ambient environment of erbium caused by thermal annealing. It is thought that the intensity of the Er PL should change critically with the change in the chemical environment of Er3. An important role may be played by the ability of erbium to combine with nitrogen. Ionized atoms of hydrogen can diffuse effectively to ll in the network of the host matrix under the annealing temperature around 300 8C, which conduces to catalyze this course. It was already known that the annealing at 300400 8C changes the environment of Er ions, resulting in the increase in the PL intensity [12]. According the DRAE model, defect PL is an inevitable phenomenon during the Er3 excitation course, which also competes with the erbium excitation rate. Therefore, it is essential to investigate the Defect PL properties with the change of Si DBs density. This work will be presented in another paper.

erbium centers in the thermal annealing temperature range of 250350 8C. Having recognized that light element plays a fundamental role in promoting the activation of luminescence Er3 sites, we introduce nitrogen into samples. The co-dopant of nitrogen increases the defect density and weaken the excitation efciency of erbium. Temperature quenching is also attenuated with the increase of nitrogen doping content.

Acknowledgements One author of this work was partly supported by Short-term Exchange Programs at Kanazawa University of Japan.

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4. Conclusion In conclusion, the simultaneous investigation of the PL and ESR in the a-SiN:H(Er) is performed under post thermal annealing. The correlation between the intensity of the Er PL and the density of Si DBs is partially consistent with the model of DRAE. The rates of thermalization and energy transfer must be matched and both compete with recombination since the resonance window of Er3 is narrow. However, the Er3 photoluminescence intensity shows more inuence by the ambient environment optimization of