Photoluminescence and Photocatalytic studies of doped and capped ZnO and CeO2 nanomaterials

Ph.D Proposal By Manish Mittal Roll No. 950912008 Under the Supervision of Dr. O.P Pandey Professor

School of Physics and Materials Science THAPAR UNIVERSITY, PATIALA(PUNJAB)-147004

PRESENTATION OUTLINE
 Nanotechnology
 Need of capping        Literature review Gaps Objective Methodology Experimental work done so far Results and Discussion References

Nanotechnology
Deals with various structures of matter having dimensions of the order of a billionth of a meter.

Different types of nanostructures compared with bulk

Band Gap comparison

When the radius of nanoparticle approaches the size of the exciton Bohr radius,the motion of electrons and holes become confined in the nanoparticle. A created electron-hole pair can only fit into the nanoparticle when the charge carriers are in the state of higher energy. As a result the band-gap increases with decreasing particle size. Here the kinetic energy becomes quantized and the energy bands will split into discrete levels and phenomena is known as quantum size effect. These structures have very high surface to volume ratio & hence surface defects play an important role in their study.

Quantum confinement effects It is possible to engineer the electronic structure of a material, by reducing the crystal size. Quantum confinement effects are observed when the nanocrystallite size is less than the exciton Bohr radius

Eg

( nanocrystal )

2 JT 2 ! E g ( bulk )  (E g ! E g (bulk )  2 MR 2 nanocrytal

What extraordinary at nano-scale?

Physical, Chemical, Biological .........properties drastically change Why???? * Surface to volume ratio increases * Confinement of electron-hole pairs

Need for Capping

Surface passivation Control agglomeration

Various Techniques for the preperation of nanoparticles

1. Thermal Decomposition Method 2. Chemical Vapor Deposition Method 3. Sol-Gel Method 4. Spray Pyrolysis Method 5. Co-Precipitation Method

Advantages of Co-Precipitation Method

1. Simple growth process for large scale production 2. Efficient 3. Inexpensive 4. Homogeneous distribution of doped ions in the host matrix

Literature Review
Scientist Name/Year/Sample/Route Reddy et al.(2011)/ ZnO:Cu/Wet chemical method(1) Work Done XRD shows 40nm of undoped and37nm for Cu doped ZnO nanoparticles having wurtzite structure. PL studies shows decrease in green emission and increase of UV emission due to decrease in defects.TEM shows 40-50nmof particle size. Gaps Concentration of defects responsible for deep level emission could be reduced with Cu doping and it is possible to tune UV emission but the percentage of dopant required for defect reduction is not reported.

Chauhan et al. (2010)/ZnO:Cu/CoPrecipitation /(2)

XRD shows increase in particle size Reddy et al.(1) reported decreaes in with doping than undoped ZnO NPs. particle with doping but here the However, the particle size reduces particle size increase with doping. with increase in dopant concentration but still greater than undoped ZnO NPs. UV shows decrease in band gap from 3.15-2.92eV of undoped and Cu doped ZnO.

Literature Review
Scientist Name/Year/Sample/Route Work Done Gaps

Rana et al. (2010)/ZnO:Cu/ Wet chemical /(3)

XRD results shows decreaes in particle with doping than undoped ZnO NPs. SEM and EDS shows single phase NPS of doped and undoped ZnO and no other element except Zn and O respectively.

Here again the decrease in particle size is reported with doping which is contradictory to as reported by Reddy et al. PL and UV-vis spectra is not done.

Ullah et al. (2007)/ ZnO: Mn/Wet chemical/(13)

Showed that Mn doped ZnO bleaches The doping concentration proposed to MB much faster than undoped ZnO be 1% for faster degradation of MB. upon its exposure to UV light. Different dopant concentrations were not tried.

Literature Review
Scientist Name/Year/Sample/Route Work Done Gaps

Tsuzuki et al.(2009)/ZnO:Mn/Solgel/(14)

XRD shows 10nm particle size. UV is done. 3% Mn doping of 3% is reported for photocatalytic degradation of Rh-B dye.

Variation in dopant concentration is required for getting optimum dopant conc. For degradation of dye.

Singh et al.(2009)/Capped ZnO/Chemical method(6)

XRD- 12-20nm Paricle size.TG has been found to be more efficient capping agent than TEA( triethnolamine) , and Oleic acid.

Variation in concentration of capping agent is required to study their effects on PL. Energy transfer mechanism is required for tunable emission.

Comprehensive Study of Literature

Sample Synthesis route and Dopants and Concentra tion CeO2 [20] (2010) (microwave) CeO2 [21] (2001) Combustion Er ----------550nm (Green)& 660nm (Red) -----18,38 70nm & Dark clouds Dark and White PAS is done. appeard. clouds are ------------- -------------------3.1 Cubic 9nm 10nm SEM and Propylene glycol used as stabilizing agent Excitation Emission UV(Band XRD & Gap)(eV) Particle Size TEM Remarks

crystallne & white are 18nm amorphous. are more than

amorphous 38nm. CeO2 Calcia [22] (2002) 20mol% Soft solution chemical ------------------300(Trans Fluorite mittance) 50nm(Pure), 5-10nm (doped)

pH-7,11 Doping CaO with CeO2 reduce the particle size and increase UV

shielding and transparency to visible light.

Sample and Synthesis Dopants route and Concentrat ion CeO2 [6] (2002) Chemical Precipitation CeO2 [9] (2006) Co-precipitation method Ca(10,20,3 0, 40& 50%) ------------

Excitation

Emission

UV(Band Gap)(eV)

XRD & Particle Size (nm)

TEM

Remarks

------------

-----------

3.15

Calculated Lattice parameter from (h,k,l)

6nm and bigger

Lattice parameters increases upto 0.45% as particle size reduces to 6nm.

315nm (pure), 250-330nm (doped)

--------

3.20

Fluorite type 8.3nm(pure) 5.9 & Above30mol% Ca doping, 6.3nm(20 doped) & 50% sample contain CaCo3-

(pure),3.36 cubic & 3.51 (doped) 9.3nm(pure), 5.7nm (50%doped)

secondary phase and is not suitable products. for cosmetic

CeO2 [23] (2006) Sol-Gel

PtAu (Bimetallic catalyst), Pt & Au

---------

--------

-------

CeO2-16.18, 1%PtAu15.14, 0.5% 30.77, 2%Pt-13.65, 1%Pt-13.65, 1%Au-13.64 PtAu-

5-10nm

Catalytic studies are done with PtAu, Pt & Au doped CeO2

Sample

and Dopants

and Excitation

Emission

UV(Band Gap)(eV)

XRD & Particle Size (nm)

TEM

Remarks

Synthesis route

Concentration

CeO2 [24] (2006) Soft chemical solution

Calcia

doped ----------

---------

300(Trans mittance)

-----------

10-15nm Calcia doped

Non coated calcia doped ceria shows better ability UV and

silica coated

shielding

transparency to visible light region than calcia doped coated ceria

CeO2 [13] (2006) Compositehydroxide-mediated

-------------

--------------

--------

-----

Cubic

lattice 2-3nm at

constant5.411A0

The ceria particle with size less than 6nm display a very 1650C(0h),5-7nm at strong agglomeration to 1900C(48h), minimize the interface 2-4nm at 2200C (0h) energy. and 6-8nm at 2200C (120h)

CeO2 [31] (2007) Hydrothermal Synthesis

---------

----------

--------

------

Cubic 15.5nm

5-6nm (cerium 10-15nm (Cerium acetate)

Study Lattice type and lattice hydroxide), constant at 500 and 10000C.

Sample Synthesis route

and Dopants

and Excitation

Emission

UV(Band Gap)(eV)

XRD & Particle Size (nm)

TEM

Remarks

Concentration

CeO2 [20] (2008) Precursor

Sm3+

369nm

Two bands 325430nm & 260290nm

------

Fluorite Small particle size

-----------

Rod like structure without PVP and spherical particles 100nm size with PVP

growth calcinations

reported by SEM

CeO2 [22] (2009)

Silver

(0.1, ----------

-------

-------

Cubic

5-6nm (pure CeO2), 7-8nm (Doped CeO2)

SEM and EDS studies

0.25, 0.5, 0.75 & 1.0mol %)

CeO2 [32] (2009) Homogeneous Precipitation CeO2 [27] (2010) precipitation method

-----------

------

---------

-------

Cubic 13-20nm

------------

Study the variation of particle size with temp.

Fe(0,10,40,50,6 --------0,90,100%)

---------

342 (3.62)

Concludes the 10-20nm formation of

Degrade dyes like MB & CR. Max. Degradation is at 50% of Fe.

mixed oxides

Sample Synthesis route

and Dopants and Excitation Concentratio n

Emission

UV(Band Gap)(eV)

XRD & Particle Size (nm)

TEM

Remarks

ZnO [14]

Eu and Eu-Li --------(2006) codoped

------

-------

----------

---------

Particle size of 40nm has been observed with SEM. Cathodolumine-scence spectra

Precipitation method

ZnO [18] (2008) Chemical

-------------

300-320nm

410&558n 262nm m

Hexagonal wurtzite

1-3nm

Green emission is observed due to singly ionized oxygen vacancy.

ZnO [19] (2008) Precipitation ZnO [23] (2009) Wet Chemical Co-

Mn & Cu

---------

---------

3.2

--------

3-5nm

Mn ions affect the absorption characteristics more than Cu ions.

Mn

---------

---------

3.2

-----------

3-5nm

Photocatalytic

activity of

doped ZnO is more than pure ZnO

Sample Synthesis route

and Dopants

and Excitation

Emission

UV(Band Gap)(eV)

XRD & Particle Size (nm)

TEM

Remarks

Concentration

ZnO [31] (2010) Sol-Gel

Vanadium

325nm 371nm

& --

--

Wurtzite Zn3(VO4)2 and Zn2V2O7 phases also

15-20nm

Defect

produced

due

to

doping of vanadium element improve the photocatalytic activity which can further improve by varing doping concentration.

appeared, 1420nm

ZnO [33] (2010) Sol-Gel

Eu, 1,2,3%

320nm

--

--

Hexagonal wurtzite structure

---

Optical properties can be significantly improved by Eu doping.UV emission is

greatly reduced at 3% doping conc. ZnO [34] (2010) Sol-Gel ZnO [36] (2010) Precipitatio n CoSilver(0,1,2,3,4 and 5%) -------------3.3 Hexagonal,wu -------rtzite,2738nm Temperature variation 300-8000C Cs --3.263 Wurtzite --

Sample Synthesis route

and Dopants

and Excitation

Emission

UV(Band Gap)(eV)

XRD & Particle Size (nm)

TEM

Remarks

Concentration

ZnO [36] (2011) Co-Precipitation

Ni(0,1,2,3,4,5 %)

---------

----------

(Undoped) 300-3.35 400-3.05 500-3.00 800-2.90 (Doped) 300-3.2 400-2.95 500-2.90 800-2.85

Wurtzite 28-37nm (8000C), 30-42nm (10000C)

-------

The

band

gap

value

of

prepared undoped and Ni doped ZnO Nps reduced as annealing temp.increased upto 8000C

Gaps in present study

Doped and undoped ZnO nanoparticles have been studied for their photoluminescence and photocatalytic applications but capping with emissive polymers like PVP, Thioglycerol, Chitosen etc. on surface along with different dopants is not done in detail. Capping emissive polymers results in tunable emission but their effect on ZnO and doped ZnO nanoparticles is required for their possible use as optoelectronic materials. From literature survey of doped CeO2 nanoparticles, it appears doped CeO2 systems have been investigated but the doping effect in ceria nanoparticles with well characterized size is not done previously. The doping of ceria at that small size can be very beneficial to further improve its catalytic properties. Doping with various dopants (Ag, Ca, Er, Fe, Pt, Au, CaO, Sm etc.) in CeO2 has been done but their photocatalytic studies are not available in detail. In some cases dopants concentration increase and sometimes they reduce the photocatalytic activities. When dopants changes Ce4+ to Ce3+ they are useful for the UV filteration and if they are not transforming Ce4+ to Ce3+ then they can be used for degradation of dye. So detailed study is needed on the dopant concentration required for UV filteration and degradation of dye.

Objectives
1. To synthesize Mn and Cu doped and capped ZnO nanomaterials by chemical precipitation route.

2. To study the effect of capping agents like PVP and Chitosen on UV and PL properties. 3. To synthesize Ca and Er doped and undoped CeO2 nanomaterials. 4. To study effect of dopants on conversion of Ce4+ to Ce3+ which results in shifting of catalytic properties useful in UV filtration applications. 5. To study their photocatalytic and photoluminescence properties using UVvisible, PLE and PL spectroscopy. 6. To study morphological studies for structural and size measurement using XRD, SEM, TEM etc.

Methodology

ZnO and CeO2 nanostructures will be fabricated using chemical routes. ZnO will be doped with Mn and Cu whereas CeO2 will be doped with Ca and Er respectively. Capping agents like PVP, Merceptoethanol, Thioglycerol, Chitosen etc. will be tried to passivate the surface. ZnO and CeO2 nanostructures will be characterized by using XRD, TEM, SAED, Photoluminescence spectroscopy, UV- visible absorption and reflectance spectroscopy, EDS etc.

Work Done.
ZnO nanoparticles were synthesized by chemical precipitation technique by adding appropriate amount of zinc acetate and sodium hydroxide. 0.5 M Zinc acetate sol. In aqueous medium were added in 1% Thioglycerol(TG) and then 0.5 M sodium hydroxide was added drop wise and stirred continuously. The precipitate soon appears after the addition of sodium hydroxide and they were filtered using Whatman 40 filter paper. The particles were washed several time with ethanol and were dried at 3000C in vacuum.

Work Done
Zinc acetate NaOH
Homogeneous sol.

FLOW CHART

Mixing

Autoclave agent Capping

Magnetic stirring Washing, Filtration , Vacuum oven drying

Colloidal Sol.

Capped ZnO nanoparticles

Characterization

Morphological

Optical

Results and Discussion

Morphological Characterization and Nano-size confirmation
2000

(a)

101

Counts

For XRD Rigaku, model D maxIIIC diffractometer with Cu K radiation is used. Using Scherrer formula d =0.89 / cos Average crystallite size of ~13nm and ~16nm for capped and uncapped ZnO nanoparticles is obtained having hexagonal wurtzite structure.

Uncapped ZnO NPs TG capped ZnO NPs Wurtzite ZnO

1500

110
1000

002 100 102

103

112

500

201 200

0 30 40 50 60 70 80

Angle(2U)

XRD pattern of and uncapped (a) and (b)TG capped ZnO nanoparticles

Steady state PL spectra recorded using FlouroMax-3 (Jobin-Yvon) spectroflourometer Excitation spectra at 460nm emission
Capped ZnO
345nm

In te n s ity (a .u .)

Excitation spectra Shows excitonic peak at 345nm for both capped and uncapped ZnO Nps.Which is blue shifted than bulk ZnO which comes at 380nm.

345nm

uncapped ZnO

280 300 320 340 360 380 Wavelength(nm)

Excitation spectra of synthesized capped and uncapped ZnO nanoparticles

SEM and EDX analysis of capped ZnO nanoparticles

SEM Analysis of TG capped ZnO clearly shows the formation of ZnO Nps

EDX spectrum shows the presence of zinc and oxygen ions in larger amount along with carbon and nitrogen in less amount which is due surface adsorbed polymer TG.

Table I- EDX analysis of TG capped ZnO NPs

Element CK NK OK ZnK Wt. % 13.03 01.02 24.45 61.50 At% At.At. % % 29.90 02.01 42.14 25.94

Applications
Since common cells are almost transparent, they can hardly be seen by human eyes under optical microscope. Researchers often rely on certain fluorescence material, which attach to the interested biological component, in order to detect cell activities. Although organic fluorescent dye has been widely used to label the cells, their drawbacks, such as narrow absorption band and high chemical reactivity, are obvious compared to the nanomaterial counterparts, quantum dots (QDs), especially ZnSe, CdSe, ZnS:Mn whose emission spectra spread most of the visible wavelengths. Both biocompatibility and aqueous solubility are required for QDs to be used in biological system. Because CdSe QDs synthesized through metal-organic approach are hydrophobic, ligands exchange or extra coating are needed for those dots to use in aqueous environment. In addition, highly toxic metalorganic precursors make this complex process much less desirable than the method under development here are, which offers an easy and user-friendly way to prepare high quality CdSe QDs. ZnSe/ZnS core/shell structure QDs can be synthesized to significantly enhance the PL intensity from ZnSe so that much less QDs are needed to inject into cells to obtain strong signals. Silica coatings were also developed on the core/shell QDs to increase chemical stability and biocompatibility of the QDs. Silica coatings are also easy to functionalize by conjugating with various molecules, which can be used to track the cell activities or chemical pathways inside cells. It has been reported that PL intensity and peak wavelength of the QDs could change upon chemical bonding events of the functional molecules. The electric charges change, among others, is considered to contribute to this process. Therefore, the effect of an applied electric field, known as Stark effect, on the PL intensity and wavelength of the QDs was studied to give preliminary understanding of such phenomenon.

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Exciton Transitions in Cu Doped ZnO nanoparticles

Conduction Band
0.4eV Zni+
486nm

3.3-3.5eV 400nm
Band edge emission

418nm

527nm VZn0.61eV

0.4eV

VZn

Valance Band