CData is just a small image, you can use any image and you can resize images if necessary with imresize in the Image Processing Toolbox.
For example:
I = imread('peppers.png');
Icon = imresize(I,[16 16])
h = figure('ToolBar','none')
ht = uitoolbar(h)
hpt = uipushtool(ht,'CData',Icon,'TooltipString','Hello')